BRPI0708169B1 - Composition - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to copolymerizable copolymer dimethylone macromers containing ethylenic unsaturation and polymers obtained therefrom. The ethylenically polymerizable macromer is formed from the reaction of a copolyol dimethicone containing terminal or pendant hydroxyl groups and itaconic anhydride. The obtained macromer is homopolymerizable or copolymerizable with ethylenically unsaturated monomers and the polymers prepared therefrom are useful in a variety of industrial, home care and personal care applications.

GROUNDS

A class of silicon-containing polymers known as polydimethylsiloxanes is widely employed in the coatings and personal care industries. In coating formulations, polydimethylsiloxane and its derivatives are increasingly being used for general modification of surface properties because they provide oil water repellency, stain resistance, barrier properties, surfactant properties and lubricity. In personal care formulations, the use of polydimethylsiloxane and derivatives thereof, particularly dimethicone copolyols, has gained wide acceptance due to the surfactant characteristics of the latter and positive effect on sensory properties of a given composition.

Attempts to improve the physical properties of said formulations by incorporating dimethicone copolyols into the composition have only had limited success. These polydimethylsiloxane derivatives were often incompatible with polar polymers and / or other ingredients typically contained in coating and personal care compositions. Auxiliary additives are often required to match the polydimethylsiloxane derivative and the anionic and cationic polymers typically used in the coatings and personal care industries to prevent phase separation of key components during extended storage periods.

Thus, efforts were made to covalently incorporate the polydimethylsiloxane derivatives into the backbone of the target polymer in an effort to match the silicone and polymer components of the formulation. U.S. Patent 6,403,074 discloses a silicone-containing polymer obtained by polymerizing ethylenically unsaturated monomers in the presence of dimethicone copolyol via a free radical mechanism. The disclosure of the patent assumes that grafting of the monomers on dimethicone copolyol occurs during the polymerization reaction. However, it is not apparent from the disclosure to what extent (if at all) the copoliol dimethicone is covalently incorporated into the backbone of the polymer or whether an interpolymer of the copolyol dimethicone and the free radical polymerized monomers is formed. In the case of carbinol polyhydroxy compounds, chain transfer can often be a significant problem during free radical polymerization, and this can prevent effective copolymerization of said compounds with other ethylenically unsaturated monomers.

In another approach, silicone-containing macromers containing terminal unsaturation were synthesized via anionic polymerization of hexamethylcyclotrysiloxane monomer (D3) to form a controlled molecular weight living polymer. Termination of the anionic polymerization reaction is accomplished via the direct reaction of the living polymeric anion with halogen containing terminating agents such as chlorosilane compounds containing a polymerizable vinyl group. The vinyl-terminated siloxane-containing macromers obtained can be polymerized in turn with other copolymerizable unsaturated monomers to obtain silicone-containing copolymers as disclosed in U.S. Patent 4,693,935 and 4,728,571. However, the synthesis of these macromers is very difficult, and given the relatively high molecular weight of the macromer it is laborious to separate unreacted impurities from the reaction product.

U.S. Patent 5,162,472 discloses a vinyl terminated copolyol dimethicone macromer which is prophetically reported to be synthesized by esterification of acrylic acid with a hydroxyl terminated copolyol dimethicone. The reaction mass is heated to 140 to 180 ° C and the disclosure states that the reportedly obtained vinyl-containing silicone ester is subsequently copolymerized without further purification. As is well known, esterification of carboxylic acid with an alcohol is a slow reaction with moderate levels of oligomeric or polymeric substrates. Additionally, it is also known in the art of acrylic acid chemistry that this highly reactive monomer spontaneously dims at ambient temperatures via a thermally induced ionic mechanism and the proton dissociates from the carboxylic acid group to form a carboxylate anion which is subsequently added to acid. acrylic via Michael type addition giving the dimer.

This phenomenon is accelerated substantially at increasing temperatures. At reaction temperatures reported in the '472 development the acrylic acid starting material could rapidly dimerize by consuming most or all of this reagent giving a complex mixture of products. Since esterification of a carboxylic acid with an alcohol is slow and acrylic acid rapidly oligomerizes at reaction temperatures reported in the '472 disclosure, it is difficult to understand how the intended product is obtained.

Even if some product is formed it could be difficult, time consuming and costly to separate the desired product from the reaction mass.

A more traditional esterification procedure for the finalization of a copolyol dimethicone with a vinyl terminal group is to react an acid chloride such as acryloyl chloride with the copolyol dimethicone and employ a base to remove the released HCl. The use of acryloyl chloride eliminates the spontaneous oligomerization problems that occur with the use of acrylic acid as indicated in the '472 disclosure.

However, salt is generated as a byproduct of the esterification reaction.

Salts are also difficult to remove from macromers, but may also be detrimental to subsequent polymerization of the macromer.

In addition to the problems faced in synthesizing the previously indicated macromers, the polymerization activities of these acrylate macromers are similar to the polymerization activities of comonomers intended for polymer backbone copolymerization due to the unobstructed nature of carbon-carbon unsaturation in the vinyl group. terminal. It is common practice to vary the reactivity of the monomer as an approach to alter the polymer structure and thereby the physical and chemical properties of the latter.

Thus, there is a need for newer silicone-containing macromers that are easily synthesized and purified and which have polymerization activities that allow flexibility in copolymerization to generate copolymers with desirable properties. We have now unexpectedly verified a silicone macromer of the type referred to via a reaction originally intended to prepare easily polymerizable compounds containing the itacontact moiety. The present invention provides easily synthesized copoliol dimethicone macromers that exhibit unexpected polymerization activities that allow easy copolymerization to generate products with desirable properties. The copolyol macromers of the invention are synthesized from the reaction of a copolyol dimethicone and itaconic anhydride. Dimethicone copolyols contain terminal or pendant polyether groups that terminate in an active hydroxyl group. The reaction of a hydroxy silicone compound such as dimethicone copolyol with a cyclic anhydride is known. As disclosed in U.S. Patents 3,560,544 and 5,296,625 the reaction of the active hydroxyl group (s) on the copolyol with the anhydride gives the anhydride copolyol semester. Although these patents disclose the reaction of a copolyol dimethicone with a variety of cyclic anhydrides (including olefinically unsaturated maleic anhydride), the use of anhydrides containing exocyclic olefinic unsaturation is not described or suggested. In addition, '544 patent mentions that the derived silicone polymer is used as a surfactant, a wetting agent, detergent, emulsifier or fiber lubricant, and the disclosure of' 625 teaches that the esters obtained are useful in textile and textile applications. personal care to provide softness and lubrication on treated substrates. There is no teaching or suggestion in any of these disclosures that the reaction product of a hydroxy silicone with an anhydride containing any type of unsaturation may be employed as a polymerizable macromer in the synthesis of polymers and copolymers.

It was unexpectedly found that the itaconic anhydride reaction semi-ester (containing exocyclic unsaturation) with a dimethicone copolyol provides a mixture of various isomers of citraconate monoesters formed from the rapid isomerization of itaconic anhydride to anhydride. citraconic acid and subsequent reaction of citraconic anhydride with silicone copolyol. Most surprisingly, since the olefinic double bond in the citraconate portion of the macromer thus formed is sterically blocked by triple substitution, and the well-known fact that trisubstituted olefins do not readily polymerize via free radical at useful rates, we have found that esters of citraconate dimethicone are easily copolymerized with a variety of monomers containing free radical polymerizable olefinic unsaturation. This is an unprecedented and unexpected finding in the preparation of ethylenically unsaturated silicone copolyol esters. Itaconic anhydride is known to react with alcohols to generate the expected itaconate esters.

BRIEF DESCRIPTION OF DRAWINGS

Figure 1 is a photograph of a Caucasian-haired mannequin head in which half of the head is modeled with a hair fixative composition containing a polymer of the invention and the other half of the head is modeled with a control fixative composition. The photograph is taken before exposure in the humidity chamber.

Figure 1A is a photograph of an Asian haired mannequin head in which half of the head is modeled with a hair fixative composition containing a polymer of the invention and the other half of the head is modeled with a commercial fixative composition. The photograph is taken before exposure in the humidity chamber.

Figure 2 is a photograph of the Caucasian mannequin head illustrated in Figure 1 taken after 1 hour in a humidity chamber set at 35 ° C and 90% relative humidity.

Figure 2A is a photograph of the Asian-haired mannequin head illustrated in Figure IA taken after 1 hour in a humidity chamber set at 35 ° C and 90% relative humidity.

Figure 3 is a photograph of the Caucasian mannequin head illustrated in Figure 1 taken after 2 hours in a humidity chamber set at 35 ° C and 90% relative humidity.

Figure 3A is a photograph of the Asian-haired mannequin head illustrated in Figure 1A taken after 2 hours in a humidity chamber set at 35 ° C and 90% relative humidity.

Figure 4 is a photograph of the Caucasian mannequin head illustrated in Figure 1 taken after 3 hours in a humidity chamber set at 35 ° C and 90% relative humidity.

Figure 4A is a photograph of the Asian-haired mannequin head illustrated in Figure 1A taken after 3 hours in a humidity chamber set at 35 ° C and 90% relative humidity.

Figure 5 is a photograph of the measuring device used in the High Humidity Stiffness Curl Retention Test (HHSR), showing the graduated hair scale mounting bracket at the bottom.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

The copolyol dimethicone macromers of the present invention are obtained from isomerization of itaconic anhydride and subsequent esterification of isomerization products with a hydroxy-containing copolyol dimethicone. Itaconic anhydride contains exocyclic unsaturation as indicated in the structure below: Exocyclic unsaturation is illustrated as the carbon-carbon double bond between the ring carbon atom and the alkylidene group, e.g. e.g. methylene.

In the reaction medium comprising a copolyol dimethicone (DMC-OH) and itaconic anhydride, itaconic anhydride almost instantaneously isomerizes to citraconic anhydride which then reacts with the copolyol giving the citraconate (and its regio-e) stereoisomers). Smaller amounts of the itaconate ester regioisomers are also formed. An illustrative general reaction scheme is as follows: Smaller amounts (less than 10% by weight of the total ester formed) of the itaconate ester are formed due to a balance between citraconic anhydride and itaconic anhydride.

It should be noted that the copolyol dimethicone represented by DMC-OH contains one or more anhydride-reactive hydroxyl groups which may be located at a terminal tip (s) of the dimethicone backbone or may be located as part of one or more pendant groups on the backbone of dimethicone. Representative dimethicone copolyols are presented in Formulas I and II below. The esterification reaction may be performed with or without a catalyst. When conducting the esterification reaction without catalyst the reaction mixture is heated to reaction temperatures from about 75 ° C to about 90 ° C. The reaction may be operated with a stoichiometric amount of dimethicone copolyol (based on the OH index) and anhydride, or a slight excess of either reagent. In one embodiment of the invention, the loading amount of anhydride to dimethicone copolyol in the reaction mixture comprises from 0.1 equivalent to 1 equivalent based on the OH index of dimethicone copolyol. In another embodiment the loading of anhydride to dimethicone copoliol is between 0.25 equivalent to 0.75 equivalent based on the OH index of the copoliol, and in another additional embodiment the loading is between 0.5 equivalent to 0.75 equivalent. The reaction can be performed in 1 to 3 hours. The reaction is conducted under an inert atmosphere, such as a nitrogen blanket, and may be carried out in an appropriate solvent.

When the reaction is carried out in the presence of a esterification catalyst, the reaction rates are significantly accelerated. Conventional esterification catalysts may be used at concentrations between 0.05% and 0.50% based on the weight of the anhydride and dimethicone copolyol in the reaction mixture. Advantageous esterification catalysts include, but are not limited to, sulfuric acid, elemental tin, elemental zinc, elemental titanium, organo-titanate compounds, organo-tin compounds, organo-zinc compounds, zinc oxide, magnesium oxide, calcium, tin oxide, and alkali metal acetates such as sodium acetate and potassium acetate. Reaction temperatures may range from room temperature to about 90 ° C. Typically, room temperature comprises from about 20 ° C to about 26 ° C. All other reaction conditions are as indicated above for non-catalyzed reactions.

In another embodiment of the invention, it may be possible to use citraconic anhydride which has methyl substitution in the double bond in place of itaconic anhydride in the esterification reaction.

In one embodiment of the invention the advantageous esterification copolyol dimethicone contains a hydroxyl terminal group (s) and may be represented by Formula I below: wherein R1 and R2 independently represent a radical selected from C1 to C30 alkyl, C1 to C6 alkyl Halogen-substituted C20 (e.g., -CCl3, -CBr3, CF3), C3 to C8 cycloalkyl, C6 to C14 aryl, and C2 to C20 alkenyl; E represents a divalent ethylene radical (-CEI2CH2-); P independently represents a divalent propylene radical (-CH 2 CH (CH 3) -) or (-CH 2 CH 2 CH 2 -); a, b, and c are independently from 0 to 100; en is from 0 to 200, E taken together with the oxygen atom to which it is attached represents an ethylene oxide radical (EO or OE) and P, taken with the oxygen atom to which it is attached, represents a radical of propylene oxide (PO or OP). EO / PO radicals can be arranged in random, non-random, or block sequences. As used herein and throughout the description the terms halogen and halo include, but are not limited to, bromine, chlorine, and fluorine.

Exemplary R1 and R2 radicals include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, phenyl, vinyl, and allyl. Each of the foregoing radicals as well as the generic radicals R1 and R2 set forth above are optionally substituted by C1 to C5 alkyl, halogen, and (C1 to C5) alkyl halo (e.g., -CCI3, -CBr3, CF3).

In one embodiment of the invention the advantageous esterification copolyol dimethicone contains a pendant hydroxy group (s) and may be represented by Formula II below: wherein R3 represents a radical selected from C1 to C30 alkyl, halo (C1 to C20) alkyl (e.g., -CC 13, -CBr 3, CF 3), C 3 to C 8 cycloalkyl, C 6 to C 14 aryl, and C 2 to C 20 alkenyl; R 4 independently represents a radical selected from C 1 to C 30 alkyl, C 6 to C 14 aryl, and C 2 to C 20 alkenyl; EO (OE) and PO (OP) represent propylene oxide and propylene oxide radicals as previously defined; a, b, and c are independently from 0 to 100; x is from 0 to 200; and y is 1 to 200. EO / PO radicals can be arranged in random, non-random, or block sequences.

Exemplary R3 radicals include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, phenyl, vinyl, and allyl. Each of the foregoing radicals as well as the generic R radicals described above are optionally substituted by C1 to C5 alkyl, halogen, and (C1 to C20) halo alkyl (e.g., -CC13, -CBr3, CF3).

Exemplary R4 radicals include, but are not limited to, methyl, phenyl, and vinyl. Each of the foregoing radicals as well as the generic R4 radicals described above are optionally substituted by C1 to C5 alkyl, halogen, and (C1 to C20) alkyl halo (e.g., -CC13, -CBr3, CF3).

Advantageous esterification copolyol dimethicone reagent materials are described in U.S. Patent Nos. 5,136,063 and 5,180,843, the disclosures of which are incorporated herein by reference.

Additionally, dimethicone copolyols are commercially available under the trade names Silsoft® and Silwet® from General Electric Company (GE-OSi). Specific product designations include, but are not limited to, Silsoft 305, 430, 475, 810, 895, Silwet L 7604 (GE-OSi), and DC 5103 (Dow Corning Corporation).

An exemplary reaction scheme illustrating esterification of a copolyol dimethicone of Formula I is as follows: wherein ReR 'independently represent hydrogen and a cyclic anhydride radical (semester) represented by the formulas: and all isomers thereof; provided that ReR 'is not both hydrogen at the same time; and R1, R2, EO, OE, PO, OP, a, b, c, and n are as previously defined. The reaction product represented by Formula III will contain a mixture of dimethicone copolyol itaconates and citraconates including their regio- and stereoisomers (isomers).

An exemplary reaction scheme illustrating the esterification of a Formula II copolyol dimethicone is as follows: wherein R 'is a cyclic anhydride radical as previously defined, and, R1, R2, R3, R4, EO, (OE) , PO, (OP), a, b, c, x and y are as previously defined, and z is <y. The reaction product represented by Formula IV will contain a mixture of copolyol dimethicone citronates (mostly) and copolyol dimethicone itaconates (minor) including their isomers.

Surprisingly, it has been found that the dimethicone copolyol citraconates of Formulas III and IV wherein the ReR1 groups contain olefinic unsaturation are easily polymerizable. It has also been found that semesters formed from dimethicone copolyols and maleic anhydride are also polymerizable with a variety of copolymerizable monomers.

In one embodiment of the present invention the copolymerizable copolyol dimethicone macromers conform to the following structures: wherein R1, R2, R3, R4, EO (OE), PO (OP) ia, b, c, n, x, y and z are as previously defined; R5 and R6 are independently selected from hydrogen and methyl, provided that both R5 and R6 do not represent methyl at the same time; and R 'represents hydrogen or a radical represented by the structure: wherein R 5 and R 6 are as defined above. In one embodiment at least one of R5 and R6 in the above formulas is methyl.

In one embodiment of the invention, the copolyol dimethicone macromers presented under Formulas III, IIIa, IV, and IVa are free radical polymerizable. Polyol macromers are homopolymerizable and can be used as building blocks to create a star-shaped, comb-shaped, brush-shaped, and / or flower-shaped polymer) or are copolymerizable and can be used as building blocks to design well-defined structure, such as graft copolymers of arms, branches, rakes, combs) with ethylenically unsaturated free radical polymerizable monomers.

By ethylenically unsaturated it is understood that the monomer has at least one polymerizable carbon-carbon double bond. The macromers of this invention may be employed in polymer synthesis to provide dimethicone copolyols inherent properties to a particular polymer backbone. Such polymers may be used in personal care, textile and industrial formulations to impart softness, lubricity, sensory, fixative, conditioning, water repellent, gloss, surface, and solubility properties, just to name a few.

In one embodiment, the polymers of the invention may be polymerized from a mixture of monomers comprising (on a total monomer weight basis): (a) about 0.1 to 100% by weight of at least one copolyol dimethicone macromer selected from the following: Formulas III, IIIa, IV and IVa above; (b) from 0 to 99.9% by weight of a nonionic monomer; (c) from 0 to 99.9% by weight of at least one acid vinyl monomer; (d) from 0 to 99.9% by weight of at least one cationic vinyl monomer; (e) from 0 to 99.9% by weight of at least one associative vinyl monomer; (f) from 0 to 99.9% by weight of at least one semihydrophilic vinyl monomer; and (g) 0 to 5% by weight of a cross-linking monomer. The amount and selection of each monomer employed in the polymerizable monomer mixture will depend upon the desired properties of the polymer product. Advantageous monomers that are copolymerizable with the copolyol dimethicone macromers are described below. Although the overlapping weight ranges for the various monomer components that make up the polymerizable monomer mixture have been expressed for selected embodiments of the invention, it should be readily understood that the specific amount of each monomer component in the monomer mixture will be selected. of its disclosed range so that the desired amount of each monomer is adjusted such that the sum of all monomer components in the polymerizable monomer mixture will total 100% by weight.

Polymers may optionally be prepared from a mixture of monomers comprising one or more chain transfer agents, which are well known in the polymeric arts.

The terms "halogen substituted", "hydroxyl substituted", "carboxyl substituted", "polyoxyalkylene substituted", "alkyl substituted", and "aryl substituted" as used herein with reference to alkyl or aryl groups, and analogues mean that at least one hydrogen atom in an alkyl, aryl, or analog group has been replaced by at least one halogen atom, hydroxyl group, carboxyl group, polyoxyalkylene group, alkyl group, or aryl group, respectively. As used herein, the terms "(meth) acrylic acid", (meth) acrylate ", and" (meth) acrylamide "shall include the corresponding methyl derivatives of acrylic acid, alkyl acrylate, and acrylamide. For example, acid" (meth) acrylic "refers to acrylic acid and / or methacrylic acid," (meth) acrylate "refers to alkyl acrylate and / or alkyl methacrylate, and" (meth) acrylamide "refers to derivatives of acrylamide and / or methacrylamide.

Nonionic Vinyl Monomer Advantageous nonionic vinyl monomers for use in the present invention are ethylenically unsaturated copolymerizable nonionic monomers which are well known in the art. In one embodiment the nonionic monomers are compounds having one of the following Formulas: (V) CH 2 = C (X) Z, (VI) CH 2 = CH-0C (0) R 7; wherein, in each of formulas (V) and (VI), X is H or methyl; and Z is -C (O) R 8, -C (O) NH 2, -C (O) NHR 8, -C (O) N (R 8) 2, -C 6 H 4 R 8, -C 6 H 4 OR 8, -C 6 H 4 Cl, -C 6 H 7 (-C 6 H 7) R8) (R8) (R8) (e.g. tri-substituted cyclohexyl), -CN, -NHC (O) CH3, -NHC (O) H, N- (2-pyrrolidonyl), N-caprolactamyl, - C (0) NHC (CH 3) 3, -C (0) NHCH 2 CH 2 -N-ethylenurea, - Si (R 7) 3, -C (0) 0 (CH 2) x Si (R 7) 3, -C (0) NH ( CH 2) x Si (R 7) 3, or - (CH 2) x Si (R 7) 3; x is an integer in the range 1 to about 6; each R7 is independently straight and branched C1 to C18 alkyl; each R 8 is independently straight and branched C 1 to C 30 alkyl, hydroxy substituted C 2 to C 30 alkyl, or halogen substituted C 1 to C 30 alkyl.

Nonlimiting examples of advantageous nonionic monomers include C1 to C30 alkyl (meth) acrylates; cyclohexyl (meth) acrylates; 3,3,5-trimethylcycloexyl (meth) acrylates (TMCHMA); C 1 to C 30 alkyl (meth) acrylamides; styrene; substituted styrenes, such as vinyl toluene (e.g., 2-methyl styrene), butyl styrene, isopropyl styrene, p-chloro styrene, and the like; vinyl esters, such as vinyl acetate, vinyl butyrate, vinyl caprolate, vinyl pivalate, vinyl neodecanoate, and the like; unsaturated nitriles, such as methacrylonitrile, acrylonitrile, and the like; and unsaturated silanes such as trimethylvinylsilane, dimethylethylvinylsilane, allyl dimethylphenylsilane, allyltrimethylsilane, 3-acrylamidopropyltrimethylsilane, 3-trimethylsilylpropyl methacrylate, and the like. Nonlimiting examples of advantageous water-soluble nonionic monomers are C1 to C6 hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (2-HEA), 3-hydroxypropyl acrylate; glycerol mono (meth) acrylate; tris (hydroxymethyl) ethane mono (meth) acrylate; pentaerythritol mono (meth) acrylate; N-hydroxymethyl (meth) acrylamide; 2-hydroxyethyl (meth) acrylamide; 3-hydroxypropyl (meth) acrylamide; (meth) acrylamide; t-octyl (meth) acrylamide; N- (2,3-dihydroxypropyl) acrylamide; t-butyl (meth) acrylamide; N-vinyl caprolactam; N-vinyl pyrrolidone; methacrylamidoethyl-N-ethylenurea (e.g. CH2 = C (CH3) C (0) NHCH2CH2-N-ethylenourea), (meth) acrylates and C1-4 alkoxy substituted (meth) acrylamides such as methoxyethyl (meth) ) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, and the like; and combinations thereof.

Other useful nonionic vinyl monomers include allyl alcohol, glycerol monoallyl ether, 3-methyl-3-buten-1-ol, and vinyl alcohol precursors and equivalents such as vinyl acetate.

Advantageous Vinyl Monomer Advantageous acid vinyl monomers for use in the present invention are polymerizable, ethylenically unsaturated acid monomers preferably containing at least one carboxylic acid, sulfonic acid group, or phosphonic acid group to provide an acidic or functional site. anionic. These acid groups may be derived from monoacids or diacids, dicarboxylic acid anhydrides, diacid monoesters, and salts thereof.

Advantageous acid monomers containing vinyl carboxylic acid include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, and the like, and C1 to C6 alkyl monoesters of maleic acid , fumaric, itaconic, or aconitic, such as hydrogen methyl maleate, monoisopropyl maleate, butyl hydrogen fumarate, and the like.

Dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and the like can also be used as acid vinyl monomers. Such anhydrides generally hydrolyze to the corresponding diacids upon prolonged exposure to water or at high pH.

Advantageous sulfonic acid group monomers include, but are not limited to, vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS, 2-acrylamido-2-methylpropane sulfonic acid), allyloxybenzene acid sulfonic, and the like. Particular preference is given to the sodium salt of styrene sulfonic acid (SSSA) and AMPS.

Nonlimiting examples of advantageous phosphonic acid group-containing monomers include vinyl phosphonic acid, allyl phosphonic acid, 3-acrylamidopropyl phosphonic acid, and the like.

Advantageous salts include, but are not limited to, alkali metal salts such as sodium, potassium and lithium salts; alkaline earth metal salts such as calcium and magnesium salts; ammonium salts; and alkyl-substituted ammonium salts, such as 2-amino-2-methyl-1-propanol (AMP) salts, ethanolamine, diethanolamine, triethanolamine, triethylamine, and the like.

The foregoing monomers or salts thereof may be used as the vinyl acid monomer component in mixtures of two or more.

Cationic Vinyl Monomer Advantageous cationic vinyl monomers for copolymerization are basic, polymerizable, ethylenically unsaturated monomers preferably containing at least one functional amino group.

These basic amino groups may be derived from mono-, di- or polyamino alkyl groups or nitrogen-containing heteroaromatic groups. The amino group may comprise primary, secondary or tertiary amines. The monomers may be used in amino or salt form as desired.

Nonlimiting examples of advantageous cationic monomers may be selected from: a mono- (C1 to C4) alkylamino (C1 to Cg) alkyl (meth) acrylate, a di- (C1 to C4) alkylamino (C1 to Cgjalkyl (meth) acrylate a mono- (C1 to C4) alkylamino (C1 to C8) alkyl (meth) acrylamide, a di- (C1 to C4) alkylamino (C1 to C8) alkylamino, a nitrogen-containing heterocyclic (meth) acrylamide, a nitrogen containing heterocyclic (meth) acrylate, and mixtures thereof.

Specific examples of advantageous cationic monomers include, but are not limited to, 2- (N, N-dimethylamino) ethyl (meth) acrylate (DMAEMA), 3- (N, N-dimethylamino) propyl (meth) acrylate, 4- (N, N-dimethylamino) butyl (meth) acrylate, (N, N-dimethylamino) t-butyl (meth) acrylate, 2- (t-butylamino) ethyl (meth) acrylate (TBAEMA), 2- (N, N-diethylamino ) ethyl (meth) acrylate (DEAEMA), 3- (N, N-diethylamino) propyl (meth) acrylate, 2- (N, N-dimethylamino) neopentyl acrylate (DMANPA), 4- (N, N-diethylamino) butyl (meth) acrylate, 2- (N, N-dipropylamino) ethyl (meth) acrylate, 3- (N, N-dipropylamino) propyl (meth) acrylate, 4- (N, N-dipropylamino) butyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl acrylate, N '- (2-N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-dimethylamino) propyl (meth) acrylamide (DMAPMAm), N '- (3-N, N-dimethylamino) propyl (meth) acrylamide, N- (2-pyridyl) acrylamide , N- (2-imidazoyl) (meth) acrylamide, N- (4-morpholinyl) (meth) acrylamide, N- (4-morpholinyl) acrylamide, 2-vinyl pyridine, 4-vinyl pyridine, N-vinyl-2-methylimidazole, N-vinylimidazole, N-vinyl-4-methylimidazole, and N-vinyloxazolidone, and mixtures thereof.

Advantageous salt forms of the cationic monomers include, but are not limited to, mineral acid salts such as the hydrochloride, sulfate, C1 to C30 alkyl sulfate and phosphate salts; and organic acid salts, such as acetate, maleate, and fumarate salts; and analogs.

Non-limiting examples of salt forms of cationic monomers include, but are not limited to, 3-trimethylammonium propyl methacrylamide chloride, 3-trimethylammonium propyl acrylamide chloride, Ν, et-dimethylaminoethyl methacrylate quaternized using C1 to C30 alkyl sulfate, methacrylate Î ±, Î ± -dimethylaminoethyl quaternized using methyl chloride, chromized vinyl imidazole, methacryloyl ethyl betaine, and methacryloyl N-oxide.

Associative Vinyl Monomer Advantageous associative vinyl monomers (hydrophobic monomer) for use in polymer synthesis are compounds having a portion of ethylenically unsaturated terminal group (i) for polymerization by addition with the other monomers of the mixture; a mid-section portion of polyoxyalkylene (ii) for imparting selective hydrophilic properties to the polymer product and a portion of hydrophobic terminal group (iii) for conferring selective hydrophobic properties to the polymer. The portion (i) providing the ethylenically unsaturated terminal group is preferably derived from an ethylenically unsaturated mono or dicarboxylic acid or anhydride thereof, more preferably a C3 or C4 mono or dicarboxylic acid. or the anhydride thereof. Alternatively, portion (i) of the associative monomer may be derived from an allyl ether or vinyl ether; a vinyl substituted nonionic urethane monomer as disclosed in U.S. Patent No. 33,156 or U.S. Patent 5,294,692; or a vinyl substituted urea reaction product as disclosed in U.S. Patent 5,011,978; whose relevant disclosures are incorporated herein by reference. The mid-section portion (ii) is preferably a polyoxyalkylene segment of from about 5 to about 250, more preferably from about 10 to about 120, and most preferably from about 15 to about 150. to about 60 repetitive units of C 2 to C 7 alkylene oxide.

Preferred mid-section portions (ii) include polyoxyethylene, polyoxypropylene, and polyoxybutylene segments comprising from about 5 to about 150, more preferably from about 10 to about 100, and most preferably from about 15 to about 60 units of ethylene, propylene or butylene oxide; and random or non-random sequences of units of ethylene oxide, propylene oxide and or butylene oxide. The hydrophobic terminal group portion (iii) of the associative monomers is preferably a hydrocarbon moiety belonging to one of the following hydrocarbon classes: a linear alkyl of from Cg to C40, an aryl substituted C2 to C40 alkyl, a phenyl with from C 2 to C 40 substituted by alkyl, a branched alkyl of from Cg to C40, a carbocyclic alkyl of from Cg to C40; and a C8 to C8 complex ester. Complex esters are formed by esterifying a polyol with a long chain hydroxy acid containing both a hydroxyl group and also a carboxylic group. The long chain hydroxy acid carboxylic group reacts with at least one polyol hydroxyl group. In turn, the hydroxyl group of the long chain hydroxy acid reacts with a carboxylic group of another long chain hydroxy acid and / or another long chain carboxylic acid.

By long chain is meant that hydroxy acid and carboxylic acid contain from about 10 to 30 carbon atoms. The carbon chain may be saturated or unsaturated. Exemplary non-limiting examples of an advantageous polyol are glycerol, sorbitol, pentaerythritol, trimethylol propane. An exemplary nonlimiting example of a hydroxy acid is 12-hydroxy stearic acid. Exemplary non-limiting long chain carboxylic acids are those which are the fatty acids derived from vegetable oils and fatty acids presented herein.

Nonlimiting examples of advantageous hydrophobic terminal group moieties (iii) of the associative monomers are straight or branched alkyl groups having from about 8 to about 40 carbon atoms, such as capryl (C8), isooctyl (branched C8), decyl ( (C10), (C12) lauryl, (C14) myristyl, (C16) cetyl, (C16 to C19) cetearyl, (C18) stearyl, (C18) isostearyl, (C20) arachidyl, C22) silyl, (C24) lignoceryl , C26 cerotyl, C28 montanyl, C30 melissila, C32 laceryl, and the like.

Examples of straight and branched alkyl groups having from about 8 to about 40 carbon atoms that are derived from a natural source include, but are not limited to, alkyl groups derived from hydrogenated peanut oil, soybean oil and canola oil ( all predominantly C 18), hydrogenated talol oil (C 16 to C 18), and the like; and hydrogenated C10 to C20 terpenols such as hydrogenated (C10 branched) geraniol, hydrogenated (C15 branched) famesol, hydrogenated (C20 branched) phytol, and the like.

Nonlimiting examples of advantageous C 2 to C 40 alkyl substituted phenyl groups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl, octadecylphenyl, isooctylphenyl, s-butylphenyl, and the like.

Advantageous C8 to C40 carbocyclic alkyl groups include, but are not limited to, sterol-derived groups from animal sources such as cholesterol, lanosterol, 7-dehydrocholesterol, and the like; from plant sources such as phytosterol, stigmasterol, campesterol, and the like; and from yeast sources such as ergosterol, mycosterol, and the like. Other hydrophobic carbocyclic alkyl terminal groups useful in the present invention include, but are not limited to, cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and groups derived from natural carbocyclic materials, such as pinene, hydrogenated retinol, camphor, isobomyl alcohol, and the like.

Exemplary aryl substituted C 2 to C 40 alkyl groups include, but are not limited to, styryl (e.g. 2-phenylethyl), distyryl (e.g. 2,4-diphenylbutyl), trystyryl (e.g. 2 , 4,6-triphenylhexyl), 4-phenylbutyl, 2-methyl-2-phenylethyl, trystyrylphenolyl, and the like.

Nonlimiting examples of advantageous C6 to C8 complex esters include hydrogenated castor oil (predominantly 12-hydroxostearic acid triglyceride); 1,2-diaryl glycerols, such as 1,2-distearyl glycerol, 1,2-dipalmityl glycerol, 1,2-dimyristyl glycerol, and the like; di-, tri-, or sugar polyesters, such as 3,4,6-tristearyl glucose, 2,3-dilauryl fructose, and the like; and sorbitol esters, such as those described in U.S. Patent 4,600,761 to Ruffher et al., which disclosures that are pertinent are incorporated herein by reference.

Useful associative monomers may be prepared by any method known in the art. See, for example, U.S. Patent 4,421,902 to Chang et al .; No. 4,384,096 to Sonnabend; No. 4,514,552 to Shay et al .; No. 4,600,761 to Ruffher et al .; No. 4,616,074 to Ruffher; No. 5,294,692 to Barron et al .; No. 5,292,843 to Jenkins et al .; 5,770,760 to Robinson; and No. 5,412,142 to Wilkerson, III et al; whose pertinent disclosures are incorporated herein by reference.

Examples of associative vinyl monomers include those represented by the following Formula (VII): wherein each R 9 is independently H, C 1 to C 30 alkyl, -C (O) OH, or -C (O) OR 10; R10 is C1 to C30 alkyl; A is -CH 2 C (O) 0-, -C (O) 0-, -O-, -CH 20 -, -NHC (O) NH-, -C (O) NH-, -Ar- (CE 2) z- NHC (O) 0-, -Ar- (CE2) Z -NHC (O) NH-, or -CH 2 CH 2 NHC (O) -; Ar is a divalent arila; E is H or methyl; z is 0 or 1; k is an integer in the range 0 to about 30, m is 0 or 1, provided that when k is 0, m is 0, and when k is in the range 1 to about 30, m be 1; (Rn-O) n is a polyoxyalkylene which is a homopolymer, a random copolymer, or a C2 to C4 oxyalkylene unit block copolymer, wherein R11 is C2H4, C3H6 (and isomers), C4H8, or a mixture thereof, and n is an integer in the range of from about 5 to about 250, preferably from about 5 to about 100, more preferably from about 10 to about 80, and most preferably from about 15 to about 60; Y is -RnO-, -RnNH-, -C (O) -, -C (O) NH-, -RnNHC (O) NH-, or -C (O) NHC (O) -; and R12 is a substituted or unsubstituted alkyl selected from the group consisting of a linear C8 to C40 alkyl, a branched C8 to C40 alkyl, a C8 to C40 carbocyclic alkyl, a C2 to C40 phenyl substituted by alkyl, an aryl-substituted C 2 to C 40 alkyl, and a C 8 to C 80 complex ester; wherein R11 alkylene and R12 alkyl group optionally includes one or more substituents selected from a hydroxyl group, a C1 to C5 alkoxy group, and a halogen group.

Specific examples of associative vinyl monomers of Formula (VII) include polyethoxylated cetyl methacrylate (CEM), polyethoxylated cetearyl methacrylate (CSEM), polyethoxylated (meth) acrylate of arachidyl polyethoxylated methacrylate (methacrylate) BEM), polyethoxylated lauryl methacrylate (LEM), polyethoxylated (meth) acrylate, kerotyl (meth) polyethoxylated (meth) acrylate, polyethoxylated (meth) acrylate (meth) acrylate (meth) acrylate TEM), hydrogenated castor oil polyethoxylated methacrylate (HCOEM), polyethoxylated canola (meth) acrylate, and polyethoxylated cholesterol methacrylate (CHEM), where the polyethoxylated portion of the monomer comprises from about 5 to about 100, preferably, from about 10 to about 80, and more preferably from about 15 to about 60 repetitive units of ethylene oxide.

Semihydrophobic Vinyl Monomer As used herein the term semihydrophobic vinyl monomer refers to compounds having two portions: (i) an ethylenically unsaturated terminal group portion for polymerization by addition with the other monomers of the reaction mixture, and (ii) a polyoxyalkylene moiety to attenuate associations between hydrophobic groups of the polymer or hydrophobic groups of other materials in a polymer-containing composition. A semihydrophobic vinyl monomer has a similar structure to the associative vinyl monomer shown above, but has a substantially non-hydrophobic end group and thus does not confer any polymer associative properties.

In one aspect, the portion of the unsaturated terminal group (i) providing the vinyl terminal group or other ethylenically unsaturated terminal group for addition polymerization may be derived from an ethylenically unsaturated mono or di-carboxylic acid or anhydride thereof, such as for example a C3 or C4 mono or di-carboxylic acid or anhydride thereof. Alternatively, in another aspect, the terminal group moiety (i) may be derived from an allyl ether, vinyl ether or a nonionic unsaturated urethane. The polymerizable unsaturated terminal moiety (i) may also be derived from an unsaturated C8 to C30 fatty acid group containing at least one free carboxy functional group. This group of C8 to C30 is part of an unsaturated terminal group moiety (i) and is different from hydrophobic groups pendant to associative monomers, which are specifically separated from the unsaturated terminal group of associative monomer by a "spacer" portion hydrophilic. The polyoxyalkylene moiety (ii) specifically comprises a long chain polyoxyalkylene moiety which is substantially similar to the hydrophilic moiety of the associative monomers. Preferred polyoxyalkylene moiety (ii) includes polyoxyethylene, polyoxypropylene, and polyoxybutylene moieties comprising from about 5 to about 250, and preferably from about 10 to about 100 oxyalkylene units.

When the semihydrophobic vinyl monomer comprises more than one type of oxyalkylene unit, the units may be arranged in random, non-random or block sequences.

In one embodiment, exemplary semihydrophobic vinyl monomers include at least one compound represented by one of the following formulas (VIII) or (IX): wherein in each of Formulas VIII and IX, R9, R11, A, k , m, and n are as previously described; D is a C 8 to C 30 unsaturated alkyl, or a C 8 to C 30 unsaturated alkyl substituted by carboxy; and R is H or C1 to C4 alkyl.

In one embodiment, the semihydrophobic vinyl monomers include monomers having the following formulas: CH2 = CH-0 (CH2) aO (C3H60) b (C2H40) cHor CH2 = CH-CH20 (C3H60) d (C2 ^ 0) eH ; where a is an integer of 2, 3, or 4; b is an integer in the range of from 1 to about 10 in one aspect, from 2 to about 8 in another aspect, and from about 3 to about 7 in another additional aspect; c is an integer in the range of from about 5 to about 50 in one aspect, from about 8 to about 40 in another aspect, and from about 10 to about 30 in another additional aspect; d is an integer in the range of from 1 to about 10 in one aspect, from about 2 to about 8 in another aspect, and from about 3 to about 7 in another additional aspect; and e is an integer in the range of from about 5 to about 50 in one aspect, and from about 8 to about 40 in another aspect.

Exemplary examples of semihydrophobic vinyl monomers include commercially available polymerizable emulsifiers under the tradename EMULSOGEN® R109, R208, R307, RAL109, RAL208, and RAL307 marketed by Clariant Corporation; BX-AA-E5P5 marketed by Bimax, Inc .; and MAXEMUL® 5010 and 5011 sold by Uniqema; and combinations thereof. Particularly preferred SVS monomers include EMULSOGEN® R208, R307, and RAL307.

EMULSOGEN® RI 09 is a randomly propoxylated / ethoxylated 1,4-butanediol vinyl ether of the empirical formula CH2 = CH-O (CH2) 4O (C3H6O) 4 (C2H4O) 10H; EMULSOGEN® R208 is a randomly propoxylated / ethoxylated 1,4-butanediol vinyl ether of the empirical formula: CH2 = CH-0 (CH2) 40 (C3H60) 4 (C2H40) 2oH; EMULSOGEN® R307 is a randomly propoxylated / ethoxylated 1,4-butanediol vinyl ether of the empirical formula: CH2 = CE1-0 (CH2) 40 (C3H60) 4 (C2H40) 3oH; EMULSOGEN® RALI 09 is a randomly propoxylated / ethoxylated allyl ether of the empirical formula CH2 = CHCH2O (C3H6O) 4 (C2H4O) 10H; EMULSOGEN® RAL208 is a propoxylated / ethoxylated allyl ether randomized with the empirical formula CH2 = CHCH20 (C3H60) 4 (C2H40) 2oH; EMULSOGEN® RAL307 is a propoxylated / ethoxylated allyl ether randomized with the empirical formula CH2 = CHCH20 (C3H60) 4 (C2H40) 3oH; MAXEMUL® 5010 is a carboxyl-functional C 12 to C 15 alkenyl hydrophobe, ethoxylated with about 24 ethylene oxide units; MAXEMUL® 5011 is a carboxyl-functional C 12 to C 15 alkenyl hydrophobe, ethoxylated with about 34 ethylene oxide units; and BX-AA-E5P5 is a randomly propoxylated / ethoxylated allyl ether of the empirical formula CH2 = CHCH20 (C3H60) 5 (C2H40) 5H.

Crosslinker Monomer The polymers of the present invention may be prepared from a mixture of monomers comprising one or more crosslinker monomers for introducing branching and controlling molecular weight.

Advantageous polyunsaturated crosslinkers are well known in the art.

It is also possible to use monounsaturated compounds bearing a reactive group which is capable of causing a formed copolymer to be crosslinked before, during or after polymerization has taken place. Other useful crosslinking monomers include polyfunctional monomers containing multiple reactive groups, such as epoxide groups, isocyanate groups, and hydrolysable silane groups. Various polyunsaturated compounds can be used to generate a partially or substantially cross-linked three-dimensional crosshair.

Examples of advantageous polyunsaturated crosslinker monomer components include, but are not limited to, polyunsaturated aromatic monomers such as divinylbenzene, divinyl naphthylene, and trivinylbenzene; polyunsaturated alicyclic monomers such as 1,2,4-trivinylcycloexane; difunctional italic acid esters such as diallyl phthalate; polyunsaturated aliphatic monomers, such as dienes, trienes, and tetraenes, including isoprene, butadiene, 1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene; and analogs.

Other advantageous polyunsaturated crosslinker monomers include polyalkenyl ethers, such as triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaalyl sucrose, and trimethylolpropane diallyl ether; polyunsaturated esters of polyalcohols or polyacids such as 1,6-hexanediol di (meth) acrylate, tetramethylene tri (meth) acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, tri (meth) acrylate. trimethylolpropane, trimethylolpropane di (meth) acrylate, and polyethylene glycol di (meth) acrylate; alkylene bisacrylamides, such as methylene bisacrylamide, propylene bisacrylamide, and the like; hydroxy and carboxy derivatives of methylene bisacrylamide, such as methylene α, β'-bismethylol bisacrylamide; polyethylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate; unsaturated polysilanes such as dimethyldivinylsilane, methyltrivinylsilane, alyldimethylvinylsilane, diallyldimethylsilane, and tetravinylsilane; polyunsaturated stannanes such as tetraalyl tin and diallyldimethyl tin; and analogs.

Useful monounsaturated compounds bearing a reactive group include N-methylolacrylamide; N-alkoxy (meth) acrylamide, wherein the alkoxy group is C1 to C6 alkoxy; and unsaturated hydrolysable silanes, such as triethoxyvinylsilane, trisisopropoxyvinylsilane, and 3-triethoxysilylpropyl methacrylate; and analogs.

Useful polyfunctional cross-linking monomers containing multiple reactive groups include, but are not limited to, hydrolysable silanes such as ethyltriethoxysilane and ethyltrimethoxysilane; epoxy substituted hydrolysable silanes, such as 2- (3,4-epoxycycloexyl) ethyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane; polyisocyanates such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,4-phenylenediisocyanate, and 4,4'-oxybis (phenylisocyanate); unsaturated epoxides such as glycidyl methacrylate and allyl glycidyl ether; polyepoxides such as diglycidyl ether, 1,2,5,6-diepoxyhexane, and diglycidyl ethylene glycol ether; and analogs. Particularly useful are polyunsaturated crosslinkers derived from ethoxylated polyols such as diols, triols and bisphenols, ethoxylated with from about 2 to about 100 moles of ethylene oxide per mol of hydroxyl functional group and terminated with a polymerizable unsaturated group such as vinyl ether, allyl ether, acrylate ester, methacrylate ester, and the like. Examples of said crosslinkers include bisphenol A ethoxylated di (meth) acrylate; bisphenol F ethoxylated di (meth) acrylate, ethoxylated tri (meth) acrylate trimethylol propane, and the like. Other ethoxylated crosslinkers useful in the polymers of the present invention include ethoxylated polol-derived crosslinkers disclosed in U.S. Patent 6,140,435 to Zanotti-Russo, the pertinent disclosures of which are incorporated herein by reference.

Non-limiting examples of crosslinker monomers are polyol acrylate and methacrylate esters having at least two acrylate or methacrylate ester groups such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated (15) triacrylate (trimethylolpropane dimethacrylate) triethylene glycol (TEGDMA), ethoxylated bisphenol A (30) dimethacrylate (EOBDMA), and the like.

Chain Transfer Agent Advantageous chain transfer agents (CTAs) for use in this invention, without limitation thereto, are selected from a variety of thio and disulfide containing compounds, such as C1 to Qg alkyl mercaptan, acid mercaptocarboxylic esters, mercaptocarboxylic esters, thioesters, alkyl Q to Qg disulfides, aryl disulfides, polyfunctional thiols, and the like; phosphites and hypophosphites; haloalkyl compounds such as carbon tetrachloride, bromotricloromethane, and the like; and unsaturated chain transfer agents, such as alpha methylstyrene.

Polyfunctional thiols include trifunctional thiols such as trimethylolpropane tris- (3-mercaptopropionate), tetrafunctional thiols such as pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tetra- (thioglycolate), and pentaerythritol tetra- (thiolact); hexafunctional thiols, such as dipentaerythritolhexa- (thioglycolate); and analogs.

Alternatively, the chain transfer agent may be any catalytic chain transfer agent that reduces the molecular weight of addition polymers during free radical polymerization of vinyl monomers. Examples of catalytic chain transfer agents include, for example, cobalt complexes (e.g. cobalt (II) chelates). Catalytic chain transfer agents can often be used at relatively low concentrations with respect to thiol-based CTAs.

In one embodiment of the invention chain transfer agents include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan (ODM), isooctyl 3-mercaptopropionate (IMP), butyl 3-mercaptopropionate, acid 3 - mercaptopropionic, butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, and the like. The chain transfer agents may be added to a mixture of reaction monomers, preferably in amounts of up to about 10% by weight of polymerizable monomer mixture, based on the total weight of the monomer mixture.

In one embodiment, the chain transfer agent is present in an amount of at least about 0.01 weight percent based on the total weight of the monomer. The copolyol dimethicone macromer of the present invention may be polymerized alone or in combination with at least one of the copolymerizable monomers from (b) to (g). Polymerization may be conducted in the optional presence of a chain transfer agent. Unsaturated monomers can be polymerized by a variety of well-known free radical polymerization techniques, such as bulk polymerization, photo polymerization, microwave polymerization, solution polymerization, suspension polymerization, emulsion polymerization, reverse emulsion polymerization. , microemulsion polymerization and the like. The ionic content of the polymers of the present invention may be influenced by adjusting the selection of monomers that are copolymerized with the copolyol dimethicone macromer in the polymer backbone. For example, an anionic, cationic and / or amphoteric monomer (and salts of these monomers) may be copolymerized into the polymer backbone to give the ionic character of the polymer. By anionic, cationic and amphoteric it is understood that the respective monomer (or monomer repetitive unit when incorporated into the polymer backbone) contains at least one ionizable portion capable of forming a salt when neutralized with an acid or base.

Examples of anionic monomers capable of imparting ionizable portions to the polymers of the invention contain the carboxylic acid and sulfonic acid groups described for the above vinyl acid monomers. Exemplary salts of these monomers / repetitive units include, but are not limited to, alkali metal and alkaline earth metal (e.g., Li, Na, K, Ca) and their ammonium salts.

Examples of cationic monomers that are capable of imparting ionizable moieties to the polymers of the invention contain the dialkylaminoalkyl moieties described for cationic vinyl monomers. Exemplary salts of these monomers / repetitive units include, but are not limited to, dialkyl sulfate (C 1 to C 18) salts (e.g., dimethyl sulfate, diethyl sulfate); hydrogen halide salts (eg hydrogen chloride, hydrogen fluoride, hydrogen bromide and hydrogen iodide); and combinations thereof.

By amphoteric is meant that the polymer backbone contains both the anionic and cationic ionizable portions above.

The respective anionic and cationic vinyl monomers may be salt-polymerized (ionized) or they may be polymerized in the polymer backbone as the anionic or cationic (nonionized) monomer and subsequently ionized by neutralization with a base or acid respectively.

In one embodiment, polymers containing anionic repetitive units may be synthesized by polymerizing a monomer composition comprising an anionic vinyl monomer selected from one or more carboxylic acid containing monomers; one or more sulfonic acid containing monomers; one or more salts of said one or more carboxylic acid containing monomers, one or more of said one or more sulfonic acid containing monomers; and combinations thereof with the desired copolyol dimethicone macromer.

In an exemplary embodiment, from 5 to 95% by weight of the polymerizable monomer composition (based on the weight of the total monomers constituting the monomer composition to be polymerized) comprises an anionic vinyl monomer selected from a monomer (s) containing carboxylic acid group, a salt of a carboxylic acid-containing monomer (s), a sulfonic acid-containing monomer (s), a salt of a sulfonic acid-containing monomer (s), and combinations thereof. In another exemplary embodiment, from 10 to 90% by weight of the monomer mixture comprises an anionic vinyl monomer selected from a carboxylic acid group-containing monomer (s), a salt of a carboxylic acid-containing monomer (s), a monomer (s) ) containing sulfonic acid, a salt of a sulfonic acid containing monomer (s), and combinations thereof.

In yet another exemplary embodiment, from 10 to 80% by weight of the polymerizable monomer composition comprises an anionic vinyl monomer selected from a carboxylic acid group-containing monomer (s), a salt of a carboxylic acid-containing monomer (s), a monomer (s) containing sulfonic acid, a salt of a sulfonic acid containing monomer (s), and combinations thereof.

In one aspect of the invention, examples of polymerizable anionic vinyl monomers that contain carboxylic acid and sulfonic acid functionality include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, fimaric acid, itaconic acid, crotonic acid, cinnamic acid , styrene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid (AMPS® monomer), and the metal ion (eg Li, Na, K, Ca) and ammonium salts thereof.

In another aspect, polymers containing cationic repetitive units may be synthesized by polymerizing a monomer composition comprising a cationic vinyl monomer selected from one or more dialkylaminoalkyl-containing group-containing monomers and salts thereof, methacrylated vinylimidazole, methacryloyl betaine, and methacryloyl N-oxide in the presence of a copolyol dimethicone macromer. More specifically, the monomer may be selected from one or more of di (C1 to C6) amino (C1 to C5) alkyl acrylates and methacrylates (and their hydrogen halide salts), and combinations thereof. The alkyl groups attached to the nitrogen atom may be the same or different (e.g. independently of each other). In an exemplary embodiment, from 5 to 95% by weight of the polymerizable monomer composition (based on the weight of the total monomers constituting the monomer composition) comprises a cationic vinyl monomer selected from one or more of di (Ci to C6) amino (Q to C5) alkyl acrylates and methacrylates and dialkyl sulfate (Q to C18) and hydrogen halide salts thereof. In another exemplary embodiment, the amount of cationic vinyl monomer comprises 10 to 90% by weight of the monomer mixture, and in an additional exemplary embodiment, the amount of cationic vinyl monomer comprises 10 to 80% by weight of the total mixture of monomers. monomers.

In a further embodiment of the invention, amphoteric polymers (e.g., the polymer backbone includes polymerized repeating units of anionic and cationic monomers and salts thereof) may be synthesized by polymerizing an amphoteric monomer composition comprising both monomers. with functionality of acid (and / or salts thereof) and dialkylaminoalkyl monomers (and / or salts thereof).

An amphoteric monomer composition comprising the anionic vinyl and cationic vinyl monomers and the salts thereof presented above can be polymerized to an amphoteric polymer. The relative amount of anionic monomer (s) to cationic monomer (s) present in the polymerizable monomer composition may comprise from 1 to 99 parts of anionic monomer (s) to 99 to 1 part cationic monomer (s). In an exemplary embodiment, amphoteric monomers comprise from 5 to 95% by weight of the total polymerizable monomer composition (based on the weight of the total monomer content of the polymerizable monomer mixture). In another exemplary embodiment, the amount of amphoteric monomer comprises from 10 to 90% by weight of the monomer mixture, and in a further exemplary embodiment the amount of amphoteric monomer comprises from 10 to 80% by weight of the total monomer mixture.

In another embodiment, nonionic polymers may be synthesized by polymerizing a mixture of nonionic monomers containing one or more of the hydrophilic monomers described above which are non-salts and which do not form salts in the presence of an acid or a base (ie, nonionic monomers). Examples of nonionic monomers include, but are not limited to, acrylamide, methacrylamide, vinyl pyrrolidone, vinyl caprolactam, and 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), 2-hydroxyethyl acrylate acrylate, hydroxypropylate (all isomers), hydroxybutyl acrylate (all isomers), polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, and combinations thereof. In an exemplary embodiment of the invention, the polymerizable monomer mixture comprises from 50 to 95% by weight (based on the weight of the total polymerizable monomer mixture) of the nonionic hydrophilic monomers. In another exemplary embodiment, the amount of hydrophilic nonionic monomer comprises from 60 to 95% by weight of the monomer mixture, and in a further exemplary embodiment the amount of hydrophilic nonionic monomer comprises from 65 to 80% by weight of the mixture. total monomers.

It should be recognized that the polymerizable monomer compositions of the invention may contain at least one monomer selected from the different classes of monomers indicated above, in combination with the copolyol dimethicone macromers of the invention.

Although overlapping weight ranges for the various monomer components that make up the polymerizable monomer mixtures of the invention have been expressed for selected embodiments of the invention, it should be readily understood that the specific amount of each monomer component in the monomer mixture will be selected from its disclosed range so that the desired amount of each monomer is adjusted such that the sum of all monomer components in the polymerizable monomer mixture will total 100% by weight.

Primers that may be used for the free radical polymerization processes of the invention are the water-soluble and water-insoluble persulfate, peroxide, organic hydroperoxides, organic peracids, and azo compounds. Advantageous initiators include, but are not limited to, ammonium persulphate, potassium persulphate, sodium persulphate, hydrogen peroxide, dibenzoyl peroxide, benzoyl peroxide, acetyl peroxide, lauryl peroxide, t-butyl perpivalate, per-2 - t-butyl ethylexanoate, di-t-butyl peroxide, di (2-ethylexyl) -peroxycarbonate, t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis (2-amidinopropane) dihydrochloride or 2, 2'-azobis (2-methylbutyronitrile), peracetic acid. Peroxides and peracids may optionally be activated with reducing agents such as sodium bisulfite or ascorbic acid, transition metals, hydrazine, and the like. Mixtures of starter systems may also be used, such as, for example, sodium sulfate / peroxodisulfate, t-butyl hydroperoxide / sodium sulfite, t-butyl hydroperoxide / sodium hydroxymethanesulfate. Primers may be employed in appropriate amounts, for example in amounts of 0.05 to 5% by weight, based on the amount of monomers to be polymerized.

In one embodiment of the invention, the polymers may be prepared using solution polymerization in a polar solvent or non-polar solvent and mixtures thereof. Exemplary solvents include, but are not limited to, water, methanol, methylene chloride, chloroform, carbon tetrachloride, ethanol, isopropanol, hexane, cyclohexane, ethyl acetate, methyl ethyl ketone and benzene, toluene, N-methyl pyrrolidone, and mixtures of these solvents. . The amounts of monomers and solvents may be selected to give from 15 to 90% by weight of monomer in solution (based on total monomer and solvent weight). Polymerization is usually carried out at temperatures from 40 to 140 ° C and atmospheric pressure or under autogenous pressure.

In another embodiment of the invention, the polymers may be synthesized via anionic and cationic emulsion polymerization techniques as is well known in the art of polymers. Typically the anionic emulsion polymerization process is carried out at a reaction temperature in the range of about 30 to about 95 ° C, however, higher or lower temperatures may be used. To facilitate emulsification of the monomer mixture, emulsion polymerization may be performed in the presence of anionic surfactants such as fatty alcohol sulfates or alkyl sulfonates, nonionic surfactants such as linear or branched alcohol ethoxylates, amphoteric surfactants, or mixtures of the same. The emulsion polymerization reaction mixture also includes one or more free radical initiators in an amount ranging from about 0.01 to about 3% by weight based on the total weight of the monomers. The polymerization may be carried out in an aqueous or aqueous alcohol medium at a low pH, i.e. preferably not above about pH 4.5.

Advantageous anionic surfactants for facilitating emulsion polymerizations are well known in the art of polymers, and include, but are not limited to, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, disodium lauret-3 sulfosuccinate, dioctyl sulfosuccinate, disodium sodium butyl naphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, branched alcohol ethoxylate phosphate esters, and the like.

In a typical cationic polymerization procedure, a mixture of stirred mixed monomers is added to an emulsifying surfactant solution, such as a nonionic surfactant, preferably a linear or branched alcohol ethoxylate, or mixtures of nonionic surfactants. and anionic surfactants such as fatty alcohol sulfate or alkyl sulfonates in a suitable amount of water in a suitable reactor to prepare a monomer emulsion. The emulsion is deoxygenated by any advantageous method, such as by spraying with nitrogen, and then the polymerization reaction is initiated by the addition of a polymerization catalyst (initiator) such as sodium persulfate or any other catalyst. advantageous free radical polymerization, as is well known in the art of emulsion polymerization. The reaction is stirred until the polymerization is complete, typically for a time in the range of about 4 to about 16 hours. The monomer emulsion may be heated to a temperature in the range of about 20 to about 80 ° C prior to addition of the initiator, if desired.

Unreacted monomer can be eliminated by adding more catalyst, as is well known in the art of emulsion polymerization. The emulsion polymerization product can then be discharged from the reactor and packaged for storage or use.

Advantageous nonionic surfactants for facilitating emulsion cationic polymerizations are well known in the art of polymers, and include, without limitation, linear or branched alcohol ethoxylates, Cg to C12 alkylphenol alkoxylates such as alkylphenol ethoxylates, block block copolymers polyoxyethylene polyoxypropylene, and the like. Other useful nonionic surfactants include Coxy to C22 fatty acid esters of polyoxyethylene glycol, mono and diglycerides, sorbitol esters and ethoxylated sorbitol esters, Glycol C8 to C22 fatty acid esters, oxide block copolymers of ethylene and propylene oxide having an HLB value above about 15, ethoxylated octylphenols, and combinations thereof.

In one aspect, alkylphenol alkoxylate surfactants include an octylphenol marketed under the tradename IGEPAL® CA-897 by Rhodia, Inc. Preferred linear alcohol alkoxylates include cetearyl alcohol polyethylene glycol ethers (a mixture of cetyl and stearyl alcohols). ) sold under the tradename PLURAFAC® C-17, PLURAFAC® A-38 and PLURAFAC® A-39 by BASF Corp. Preferred polyoxyethylene polyoxypropylene block copolymers include copolymers marketed under the trade names PLURONIC® F127, and PLURONIC® L35 by BASF Corp.

In another aspect, nonionic surfactants include ethoxylated linear fatty alcohols (50) such as DISPONIL® A 5060 (Cognis), branched alkyl ethoxylates such as GENAPOL® X 1005 (Clariant Corp.), C12 to C10 alcohol ethoxylates. Secondary Cu such as TERGITOL® SI5-30 and SI5-40 (Dow Chemical Co.), ethoxylated octylphenol-based surfactants such as TRITON® X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL® CA 407, 887, and 897 (Rhodia, Inc.), ICONOL® OP 3070 and 4070 (BASF Corp.), SYNPERONIC® OP 30 and 40 (Uniqema), ethylene oxide and propylene oxide block copolymers such as PLURONIC ® L35 and F127 (BASF Corp.), and secondary Cl1 alcohol ethoxylates such as EMULSOGEN® EPN 407 (Clariant Corp.). Many other suppliers can be found in the commercial literature.

The free radical polymerization initiators discussed above are advantageous here. Exemplary commercially available polymerization initiators include VAZO® free radical polymerization initiators available from DuPont such as VAZO® 44 (2,2'-azobis (2- (4,5-dihydroimidazolyl) propane), VAZO® 56 (2,2'-azobis (2-methylpropionamidine) dihydrochloride), and VAZO® 68 (4,4'-azobis (4-cyanovaleric acid).

Optionally, other emulsion polymerization additives, which are well known in the art of emulsion polymerization, such as buffering agents, chelating agents, inorganic electrolytes, chain terminators, defoaming agents, biocidal diluents, and pH adjusting agents may be included in the system. of polymerization.

An exemplary general emulsion anionic polymerization procedure for the preparation of alkali-swellable or acid-soluble polymer, embodiment of the present invention is given below.

A monomer emulsion is prepared in a first reactor equipped with a nitrogen inlet and a stirrer by combining a desired amount of each monomer in water containing an emulsifying amount of an anionic surfactant under a nitrogen atmosphere and stirred mix. . In a second reactor equipped with a stirrer, nitrogen inlet and feed pumps, a desired amount of water and additional anionic surfactant, if desired, is added under a nitrogen atmosphere, and the contents of the second reactor are heated with stirred mixing. After the contents of the second reactor reach a temperature in the range of about 55 to 98 ° C, a free radical initiator is injected into the thus formed aqueous surfactant solution in the second reactor, and the monomer emulsion of the first reactor is then pumped. gradually into the second reactor over a period typically in the range of about one to about four hours at a controlled reaction temperature in the range of about 45 to 95 ° C. Upon completion of the monomer addition, an additional amount of free radical initiator may be added to the second reactor, if desired, and the resulting reaction mixture is typically stored at a temperature of about 45 to 95 ° C over a period of time. sufficient time to complete the polymerization reaction. Then the resulting polymer emulsion can be cooled and discharged from the reactor.

One skilled in the polymer arts will be able to recognize that the amounts of each monomer component can be adjusted to obtain polymers having any desired ratio of monomers. Larger or smaller proportions of water may also be used as desired. It is also possible to include in the reaction mixture water-miscible solvents such as alcohols and other polymerization additives as described above. Nonionic surfactants, such as straight or branched alcohol ethoxylates, may also be added as is well known in the art of emulsion polymerization.

The polymer product emulsions may be prepared to preferably contain from about 1 percent to about 60 percent of the total polymer solids, more preferably from about 10 percent to about 50 percent of the total polymer solids. most preferably from about 15 percent to about 45 percent of total polymer solids (TS) based on the weight of the polymer.

Prior to any neutralization, polymer emulsions, as produced, typically have a pH in the range of from about 2 to no more than about 5.5, a Brookfield viscosity of not more than about 100 millipascal seconds (mPa.s ) at room ambient temperature (spindle # 2, 20 rpm) and a glaze transition temperature (Tg) of not more than about 250 ° C as determined by the method below.

Optionally, the produced polymer emulsions may be further processed by adjusting the pH to a value preferably in the range of from about 3 to about 7.5 or greater if alkaline pH is desired with alkaline materials. preferably alkali metal hydroxides, organic bases, and the like. Polymer emulsions typically swell to a viscosity greater than about 100 mPa to form viscous solutions or gels at neutral to alkaline pH, and the polymers are substantially stable at said pH values, even at pH values greater than about 100 mPa. 12. Alkali-soluble polymer emulsions can also be made soluble at neutral to alkaline pH without concomitant swelling or viscosity increase. Polymer emulsions may be diluted with water or solvent, or concentrated by evaporation of a portion of the water. Alternatively, the obtained polymer emulsion may be dried substantially to a crystalline powder or form by the use of equipment well known in the art, such as, for example, a spray dryer, a drum dryer, or a freeze dryer.

The polymers / monomers of the present invention, provided they contain ionizable groups, can be fully or partially neutralized with acids or bases before or after polymerization to adjust aqueous solubility or dispersibility. Additionally, the viscosity properties of the polymers can be adjusted by neutralizing the polymer.

Non-limiting examples of advantageous neutralizing agents for monomers and polymers carrying anionic groups are mineral bases and organic bases. Non-limiting examples of mineral bases include alkali metal hydroxides (e.g. lithium, sodium and potassium); sodium carbonate; Ammonium hydroxide; and ammonia. Non-limiting examples of organic bases, such as amino alcohols (e.g., 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, triethanolamine, triisopropylamine, tris [(2-hydroxy) -1-propylamine, 2 -amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol; diamines such as lysine; cocamine; oleamine; and morpholine.

Non-limiting examples of advantageous neutralizing agents for monomers and polymers carrying cationic groups are organic acids, including amino acids, and inorganic mineral acids. Nonlimiting examples of organic acids include acetic acid, citric acid, fimaric acid, glutamic acid, tartaric acid, lactic acid, and glycolic acid.

Non-limiting examples of mineral acids include hydrochloric acid, nitric acid, phosphoric acid, sodium bisulfate, sulfuric acid, and the like, and mixtures thereof.

The foregoing neutralizing agents may also be used as pH adjusting agents to adjust the pH of the neutralized polymer or a composition containing the neutralized polymer.

Polymers of the invention containing anionic groups and / or cationic groups may swell due to neutralization with the appropriate base or acid. These polymers can beneficially thicken acidic or basic aqueous formulations to provide aesthetically smooth textured products that flow smoothly and spread easily. The inventive multipurpose polymers can be employed as thickeners, emulsifiers, stabilizers, suspending agents, film-forming agents, fixers, conditioners, humidifiers, spreading aids, surface modifiers, gloss enhancers, and carriers to enhance effectiveness. , depositing or providing chemically and physiologically active ingredients and cosmetic materials, and as carriers for the psycho-sensory and aesthetic properties of a formulation in which they are included. The cationic character of the low pH polymers makes them useful as antistatic agents, and under certain conditions may also provide biocidal, antimicrobial, or other preservative activity.

Anionic polymer embodiments of the invention when used in combination with at least one anionic, zwitterionic, amphoteric, nonionic, cationic surfactant or combinations thereof may be formulated by the back-acid thickening technique disclosed in US Patent 6,635,702, the disclosure of which is incorporated herein by reference. The back-acid technique involves neutralizing an anionic thickening polymer with alkaline neutralizing agent to form viscosity, and then subsequently reducing the pH with an acidic pH reducing agent to the desired final pH. Viscosity and yield value generally remain unchanged or often effectively increase due to the subsequent reduction in the final pH of the formulation. This formulation technique broadens the scope of application of these polymers and provides the use of viscosity modifying anionic polymers in formulations requiring an acidic pH regime. Additionally, the back-acid thickening process can also be used to further increase the viscosity and stability of formulations formulated in the slightly acidic pH and alkaline pH regime.

At least one polymer of the present invention is added to water and mixed. The surfactant is subsequently added to the aqueous polymer solution and mixed therewith. An alkaline material is then added and mixed to raise the pH of the composition to at least about 5 in one embodiment of the invention, to at least about 6 in another embodiment, and to at least about 6.5 in an additional embodiment. The alkaline material is preferably a neutralizing agent such as sodium hydroxide, potassium hydroxide, triethanolamine, or other fatty acid amine neutralizing agent commonly used in said applications.

Alternatively, other alkaline materials such as pre-neutralized surfactants may be used. In one embodiment, the initial pH of the formulation should desirably be at least about 0.5 or 2 pH units and preferably at least 3, 4, or even 5 pH units above the target pH. end of the composition. An acidic material or pH adjusting agent is then added to reduce the pH of the composition. The material used to lower the pH of the formulation is an acidic material, and may be selected from an organic acid such as citric acid, acetic acid, alpha-hydroxy acid, beta-hydroxy acid, salicylic acid, lactic acid, glycolic acid, of natural fruits, or combinations thereof. Additionally, inorganic acids may be used, for example hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof. The amount of said acid is such that the anionic portions in the polymer backbone are sufficiently neutralized to make up the desired viscosity values. In one aspect, it may be employed from about 0.1 to about 20%, in another from about 0.2% to 15%, and in another additional aspect from about 0.25% to about 20%. 10% by weight based on the total weight of the stabilized composition. The desired ph for stabilizing compositions of the present invention obviously depends on the specific applications. Generally, personal care applications have a pH range from about 3 to about 7.5, desirably from about 4 to about 6. Generally, home care applications have a desired pH range from about 1 to about 12, and desirably from about 3 to about 10. More specifically, when using a generally insoluble perolescent or silicone compound, a desired pH is from about 5.5 to about 12, whereas when a hair dye is stabilized, the pH is from about 5 to about 9.

The cationic polymer embodiments of the invention when used in combination with at least one zwitterionic and / or amphoteric surfactant may be formulated by a back-alkaline formulation technique to obtain higher pH compositions using cationic-modifying polymers. rheology. In one embodiment of the invention, the surfactant is selected from at least one amphoteric or zwitterionic surfactant. Optionally, the cationic / surfactant polymer composition may contain other surfactants selected from anionic, nonionic, and cationic surfactants, or combinations thereof.

Formulations containing the cationic polymers of the invention in combination with an amphoteric surfactant are reduced to an initial acidic pH value using an acid neutralizing agent (to make up the desired viscosity increase) and then an adjusting agent is subsequently added. Alkaline pH is subsequently added to raise the pH value to the desired final pH value of the formulation. Viscosity, turbidity and yield value generally remain unchanged or often improve effectively. The back-alkaline formulation technique broadens the scope of application for the cationic polymers of the invention by allowing the pH increase of a formulation subsequent to the acid treatment or polymer thickening step.

Additionally, back-alkaline thickening can be used to further increase the viscosity and stability of formulated compositions in the generally accepted pH range.

In one embodiment of the invention, the one or more copolymers, cationic polymers and the like are added in water and mixed. An amphoteric and / or zwitterionic surfactant is subsequently added to and mixed with the aqueous polymer solution. If desired, optional surfactants selected from anionic, nonionic, and cationic surfactants, or combinations thereof, may be added to the formulation. Advantageous amphoteric, anionic, cationic and nonionic surfactants are described above. An acidic pH adjusting agent is then added and mixed to lower the pH of the composition to obtain the desired low pH formulation. In one aspect, the pH of the composition may be initially adjusted with an acid to a pH of from about 0.5 to about 7.0, in another aspect from about 3.0 to about 6.0, and in another additional aspect from about 4.0 to about 5.0. The acid pH adjusting agent may be selected from the organic and acid minerals described herein. In another embodiment, any acidic ingredient that is capable of reducing the initial pH of the cationic polymer composition and causing an increase in viscosity of the polymer composition is considered to fall within the scope of the invention. Acid active ingredients may be employed with or without a pH adjusting agent. Examples of advantageous acid ingredients are selected from, but are not limited to, the dermatological and cosmeceutical acid active ingredients described herein.

When citric acid is employed in the cationic polymer neutralization step (i.e., pH reduction), the viscosity of the composition effectively increases when the alkaline pH adjusting agent is subsequently added to the formulation. The pH of the acid thickened composition should desirably be at least about 1 and preferably 2 units and preferably at least 3 pH units below the final target pH of the composition. An alkaline pH adjusting agent is then added to increase the pH of the composition to the final target.

Advantageous alkaline pH adjusting agents for the back-alkaline formulation are described herein. The desired pH of the compositions of the present invention obviously depends on the specific applications of the final product. Generally, Personal Care compositions have a pH range of from about 3 to about 8.0. Generally, Home Care Compositions have a pH range of from about 1 to about 12.

Advantageously, the polymers of this invention may be employed, without limitation, in personal care products, health care products, home care products, institutional and industrial care products (collectively referred to as "i & i"), and analogs. The polymers may be employed as a film-forming conditioner, and to promote the deposition of silicone, auxiliary or conditioning agents, color cosmetics and polar and non-polar oils on skin, hair, nails, and fibers. Additionally, the polymers can be employed in industrial chemical products, textile finishing processes, printing, adhesive coating, and similar applications such as rheology modifiers, emulsifiers, stabilizers, solubilizers, suspending agents, flocculators, enhancers of gloss, surface modifiers, and pigments and grinding additives. The dimethicone copolyol-containing polymers of the invention are useful in many applications, such as thickeners and film formers in a variety of dermatological, cosmeceutical compositions employed to improve skin conditions caused by drying, light damage, aging, acne, and the like, containing conditioners, humectants, antioxidants, exfoliating agents, keratolytic agents, vitamins, and the like, typically containing an acidic active ingredient and having a pH in the range of about 0.5 to about 5.

In a cosmeceutical aspect it is possible to use a cationic polymer as a thickener for skin creams and active lotions containing, as active ingredients, Antacid, anti-cellulite, and anti-acne agents, hydroxy carboxylic acid, such as alpha- hydroxy (AHA), beta-hydroxy acid (BHA), alpha-amino acid, alpha-keto acids (AKAs), and mixtures thereof. In such cosmeceuticals, AHAs may include, but are not limited to, lactic acid, glycolic acid, fruit acids such as malic acid, citric acid, tartaric acid, extracts of natural AHA-containing compounds such as apple extract, apricot extract, and the like. , honey extract, 2-hydroxyoctanoic acid, glycolic acid (dihydroxypropionic acid), tartaric acid (hydroxypropanedioic acid), gluconic acid, mandelic acid, benzylic acid, azelaic acid, alpha lipoic acid, salicylic acid, AHA salts and derivatives, such as arginine glycolate, ammonium glycolate, sodium glycolate, arginine lactate, ammonium lactate, sodium lactate, alpha-hydroxybutyric acid, alpha-hydroxyisobutyric acid, alpha-hydroxyisovalproic acid, atrolactic acid, and the like . BHAs may include, but are not limited to, 3-hydroxy propanoic acid, beta-hydroxybutyric acid, beta-phenyl lactic acid, beta-phenylpyruvic acid, and the like.

Alpha amino acids include, but are not limited to, alpha-dicarboxylic acids, such as aspartic acid, glutamic acid, and mixtures thereof, sometimes employed in combination with fruit acid. AKAs include pyruvic acid. In some anti-aging compositions, the acid active agent may be retinoic acid, a halocarboxylic acid such as trichloroacetic acid, an acid antioxidant such as ascorbic acid (vitamin C), kojic acid, a mineral acid, phytic acid, lysophosphatidic acid, and analogues. Some acidic anti-acne actives, for example, may include salicylic acid, salicylic acid derivatives such as 5-octanoylsalicylic acid, retinoic acid, and derivatives thereof. When a cationic polymer embodiment of the invention is incorporated into the preceding acidic products, the acidic active ingredient may serve as both the active agent for skin care and as the acidic swelling agent for the cationic polymer to provide the desired viscosity.

A discussion of the use and formulation of active skin care compositions is found in COSMETICS & TOILETRIES®, C&T Ingredient Resource Series, "AHAs & Cellulite Products How They Work", published in 1995, and "Cosmeceutics", published in 1998, both obtainable from Allured Publishing Corporation, incorporated herein by reference. Compositions containing ascorbic acid-acidified alpha amino acids are described in US 6,197,317 B1, and a commercial cosmeceutical preparation using these acids in an anti-aging skin care regimen is marketed under the tradename, AFAs, by exCel Cosmeceutics (Bloomfield Hills, M1). The term "AFA", as described in the vendor's commercial literature, was coined by the developer to describe the amino acid / vitamin C combination as fruit amino acids and as the acronym for "Aminoacid Filaggrin based Antioxidants".

Other health care products in which polymers may be included are medical products such as topical and non-topical devices and pharmaceuticals. In the pharmaceutical formulation, a polymer embodiment of the invention may be employed as a thickener and / or lubricant in products such as creams, ointments, gels, pastes, ointments, tablets, gel capsules, purgative fluids (enemas, emetics, colonies, and the like), suppositories, antifungal foams, eye products (ophthalmic products such as eye drops, artificial tears, glaucoma drug supply drops, contact lens cleaners, and the like), ear products (conditioners) waxes, wax removers, ear drops, and the like), nasal products (drops, ointments, sprays, and the like), and wound care bandages (liquid bandages, wound dressings, antibiotic creams, ointments) , and the like), without limitation to them. The film-forming ability of the polymer makes the polymer particularly advantageous as a vehicle for topical medical compositions for promoting and enhancing transdermal delivery of active ingredients to the skin or across the skin to enhance the effectiveness of anti-acne and analgesic agent formulations. topical, and to control the release of drugs such as antacids from tablets, or syrups, at low pH, such as in the stomach; to control drug release from tablets, lozenges, chewables, and the like in the mildly acidic environment of the mouth; or suppositories, ointments, creams, and the like in the mildly acidic environment of the vagina; to promote the deposition of dandruff control agents from shampoos, ointments, and the like; to increase the deposition of dyes on the skin from pigmented cosmetics (makeup, lipsticks, lipsticks, and the like) and on the hair from hair dyes and the like.

In addition to the foregoing embodiments the cationic polymer of the invention at an acidic pH makes the polymer useful as a thickener for antistatic, biocidal, antimicrobial, and other preservative compositions in a variety of personal care, health care applications, and the like. , and medical. For example, the polymer may be employed as a thickener in over-the-counter (OTC) pharmaceuticals and health care products where typically cationic biocides are employed, such as oral care compositions for plaque control. and tartar, and liquid carriers containing therapeutic agents such as syrups, gels, and the like. Under certain pH controlled conditions, the cationic character of the cationic polymer of the embodiment itself may also provide antistatic activity or biocidal, antimicrobial, or preservative activity.

The polymers of the present invention may be employed, without limitation, as a lubricating coating for medical devices, such as soft tissue implants, surgical gloves, catheters, cannulas, and the like, as removable protective film coatings for medical instruments, wound dressings, and analogues, such as a mucoadhesive, particularly in the acidic environment of the stomach, as a carrier and thickener in products formulated for medical applications, such as hand sanitizer, antiviral (for anionic virus) products, antibiotic ointments, sprays and creams, non-drip sprayable disinfectants for hospitals, hard surface antimicrobial finish applied during routine maintenance, and the like.

In home care and i & i applications, the dimethicone copolyol-containing polymers of the present invention may be used, for example, as a rheology modifier, tissue conditioning agent, antistatic agent, particularly to improve formulation efficiency by means of " cling-on-surface "or enhancing the effectiveness of disinfectants, and biocidal formulations, and to synergistically improve fabric softening effectiveness in combination with traditional fabric softeners. Typical household and i & i products which may contain polymers of the invention include, but are not limited to, laundry and fabric care products such as detergents, fabric softeners (liquids or blades), ironing sprays, dry cleaning, anti-spray sprays, and stain removers and the like; hard surface cleaners for the kitchen and bathroom, and utilities and equipment employed or located on them, such as bathroom sink gels, bathtub and shower cleaners, hard water tank removers, floor and tile cleaners, wall cleaners chrome floor polishes and frames, acid-removable vinyl floor cleaners, marble and ceramic cleaners, air-cooling gels, liquid dish cleaners, and the like; disinfectant cleaners such as toilet and bidet cleaners, hand sanitizing soaps, room deodorizers, and the like.

Polymer-containing products of the present invention may contain various conventional adjuvants and additives known in the art, some of which may serve more than one function. The amounts employed will vary depending on the purpose and character of the product and can be readily determined by one of ordinary skill in the art of formulations and literature. The term "cosmetic adjuvant" includes cosmetically and pharmaceutically acceptable product finishing agents and product stabilizers that retain the physical stability of the composition and its visible aesthetic appearance and the commercial appeal over the shelf life of the composition. The term "fixative" as applied to polymers comprises the film-forming, adhesion, or coating properties deposited on the surface to which the polymer is applied. The terms "hair hold and hair styling" as commonly understood in the hair care arts, and as used herein collectively refer to hair hold agents which are hair hold and film formers which are applied topically to the hair to actively contribute to the ease of styling and / or conservation of a hairstyle, and to maintain the remodeling ability of the hairstyle.

As a result, hair fixative compositions include hair styling products, hair fixers, and hair straighteners that are conventionally applied to hair (wet or dry) in the form of gels, rinses, emulsions (oil-in-water, water-in). or multi-phase), such as lotions and creams, ointments, sprays (pressurized or non-pressurized), nozzles, foams such as hair having the hair fixative composition impregnated therein or applied to the hair so as to leave the hair fixative agent in contact with the hair for some time until it is removed, such as by washing. The term "conditioning agents", and grammatical variations thereof, as it relates to skin and hair care compositions, includes cosmetically and pharmaceutically useful materials which are humectants, humectants, and emollients. It is recognized that some conditioning agents may serve more than one function in a composition, such as emulsifying agents, lubricants, and solvents.

In one aspect of the invention, a hair care composition embodiment comprises a polymer of the present invention in an amount effective to provide the hair care composition with a property, such as a hair fixing property, a hair conditioning property, a property viscous (thickener, rheology modifier), or a combination thereof. In addition to the present polymer (s), the hair care composition may include one or more film-forming aids, hair-fixing aids, hair conditioning aids, rheology modifying aids, a structurant, or a mixture thereof, or any of the ingredients disclosed and described herein as is well known to those skilled in the art of formulating hair care products. When included in hair styling compositions, the polymers of the invention emphasize moisture resistance, stiffness, fixation, gloss, conditioning, combability, and reshaping ability when used as the sole hair-holding component or in combination with other hair-holding devices. .

A builder provides additional structure and viscosity to highly viscous creams, gels, ointments, ointments, ointments and waxy products. Structures are ingredients that are suitable for topical administration to hair and skin and are compatible with the other ingredients in a particular personal care formulation. Exemplary structuring materials include the waxes, petrolatum, fatty acids and alcohols and esters thereof, and the anionic, cationic, nonionic, and amphoteric surfactants disclosed and described herein; and mixtures thereof. In one embodiment of the invention, the structurizer may be present in an amount comprising from about 5 wt% to about 50 wt% of the total weight of the composition. In another embodiment the structurer may be present in an amount comprising from about 8 wt% to about 30 wt%.

In another embodiment of the invention, a skin care composition embodiment comprises a polymer of the present invention in an amount effective to impart to the skin care composition a property, such as a skin conditioning property, a viscous (thickener, modifier) property. rheology) or a combination thereof. Optionally, the skin care composition may include one or more skin conditioning aids, rheology modifying aids, or a mixture thereof.

Additives and adjuvant ingredients, products, or materials which may be employed in the inventive polymers discussed herein will be referred to by the international nomenclature commonly referred to as the INCI name indicated in the International Cosmetic Ingredient Dictionary, published by the Cosmetic, Toiletry, and Fragrance Association, Washington DC (hereinafter referred to as the ESfCI Dictionary), as can be found in any edition of it, for example, Volumes 1 and 2, Sixth Edition, (1995) or Volumes 1-3, Seventh and Eighth Editions, (1997, 2000) , or by their commonly used chemical names. Numerous commercial suppliers of materials listed by INCI name, trade name or both can be found in the INCI Dictionary and numerous trade publications, including, but not limited to, "2001 McCutcheon's Directories", Volume 1: Emulsifiers & Detergents and Volume 2: Functional Materials, published by McCutcheoris Division, The Manufacturing Confectioner Publishing Co., Glen Rock, NJ (2001); and 2001 Cosmetic Bench Reference, COSMETICS & TOILETRIES® edition, 115 (13), published by Allured Publishing Corporation, Carol Stream, IL (2001); whose relevant disclosures are incorporated herein by reference. Such components and the formulation of compositions are also described in detail in well-known references, such as Cosmetics Science and Technology, first edition (Sagarin (ed)), published in 1957, and second edition (Balsam, et al. (Eds)), published in 1972-74; and The Chemistry and Manufacture of Cosmetics, Second Edition (by Navarre (ed)), published in 1975, and Third Edition (Schlossman (ed)), published in 2000, both obtainable from Allured Publishing Corporation; Rieger (ed), Harry's Cosmeticology, 8th edition, Chemical Publishing, Co., Inc., New York, NY (2000); and various forms obtainable by those skilled in the pharmaceutical arts, such as Remington's Pharmaceutical Sciences, fourteenth edition, Mack Publishing Company, Easton, PA (1970); whose relevant disclosures are incorporated herein by reference. It is well known that formulated dermatological, health care, personal care and topical formulations that are applied to the skin and mucous membranes for cleaning and foaming are composed of many of the same or similar physiologically tolerable ingredients. and formulated in the same or similar product forms, differing primarily as to the purity of the selected ingredient, the presence of pharmaceutically acceptable drugs or compounds, and the controlled conditions under which products may be manufactured. Similarly, many of the ingredients employed in household products, and i & i are the same or similar to the preceding ones, differing primarily in the quantities and class of material employed. It is also well known that the selection and permitted quantity of ingredients may also be subject to governmental regulations at a national, regional, local, and international level. Thus, the discussion here of various useful ingredients for personal care and health care products may apply to household and i & i products and industrial applications. The choice and amount of ingredients in formulated compositions containing a polymer embodiment of the invention will vary depending on the product and its function, as is well known to those skilled in the formulation arts. Formulation ingredients for personal care products and topical health care products containing the polymer embodiments of the invention may typically include, but are not limited to, solvents and diluents (including water), anionic, cationic, amphoteric, and nonionic surfactants and silicone-containing derivatives thereof (such as cleaning agents, emulsifying agents, foam enhancers, hydrotropics, solubilising agents, and suspending agents); non-surfactant suspending agents; emulsifiers; emulsion stabilizers; waxes; dispersants; hair and skin conditioning agents; lubricants and slip aids; moisture barriers and softeners; humectants; humectants and the like; auxiliary rheology modifiers; viscosity adjusting agents such as solvents, electrolytes, hydrotropes, and the like; hair conditioning agents, auxiliary conditioning agents such as antistatic agents, synthetic oils, vegetable or animal oils, silicone oils, monomeric or polymeric quaternized ammonium compounds and derivatives thereof, gloss enhancers, hair binders, film formers skin protectors, binders, chelating agents, antimicrobial agents, antifungal agents, anti-dandruff agents, defoaming agents, abrasives, adhesives, absorbents, deodorizing agents; antiperspirant agents; opacifying agents; beading material (beading agents); insoluble materials, antioxidants, preservatives, propellants (water miscible or water immiscible), such as fluorinated hydrocarbons, volatile liquid hydrocarbons, compressed gases, and the like; polymer film modifying agents, such as plasticizers, tackifiers, tackifiers, wetting agents, and the like; spreading aids; sunscreen agents; sun tanning accelerators; ultraviolet light absorbers, opacifiers; acidifying and alkalizing pH adjusting agents, buffering agents, botanical extracts; dyes (temporary or permanent) such as pigments and dyes; oxidizing agents; reducing agents; hair and skin bleaching agents, pigments; beading agents, proteinaceous materials and derivatives thereof; vitamins and derivatives thereof, physiologically active agents, antiinflammatory agents, topical anesthetics, fragrance and fragrance solubilizers, and the like; and combinations thereof; in addition to previously discussed ingredients that may not appear here. Oral care products, for example, may contain anti-caries, anti-tartar and / or anti-plaque agents in addition to surfactants, abrasives, humectants, and flavorings. An extensive list of substances and their conventional functions and product categories appears in the IN Cl Dictionary, generally, and in Vol. 2, sections 4 and 5 of the seventh edition in particular, or www.ctfa-online.org incorporated herein by reference.

Below is an exemplary list of additives, adjuvants, exemplary ingredients, etc. for use in combination with the copolyol dimethicone polymers of the invention in personal care, topical skin care, home care, institutional care, and industrial care products and also in industrial processes together with exemplary amounts.

Advantageous chelators include EDTA (ethylene diamine tetraacetic acid) and salts thereof, such as disodium EDTA and tetrasodium EDTA, citric acid and salts thereof, cyclodextrins, and the like, and mixtures thereof. Advantageous chelators typically comprise from about 0.001% by weight to about 3% by weight, preferably from about 0.01% by weight to about 2% by weight, and more preferably from about 0.01%. % by weight to about 1% by weight of the total weight of the personal care compositions of the present invention.

Examples of compounds which are advantageous for use as propellants are trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, difluroethane trichlorotrifluoroethane, dimethyl ether, propane, n-butane, and isobutane, either single or mixed. Water-soluble gases such as dimethyl ether, carbon dioxide, and / or nitrous oxide may be used to obtain aerosol sprays having reduced flammability.

Water-immiscible, liquefied hydrocarbon halogenated hydrocarbon gases such as propane, butane, and chlorofluorocarbons may be advantageously used to provide the contents of an aerosol container without the drastic pressure drops associated with other immiscible gases. The top space left inside the aerosol container is not a factor because the liquefied gas rests on the aqueous composition, and the pressure inside the container is maintained at the vapor pressure of the saturated hydrocarbon vapor.

Other immiscible compressed gases such as nitrogen, helium, and fully fluorinated oxepanes and oxetanes are also useful for providing aerosol container compositions. If the propellant, such as dimethyl ether, incorporates a vapor pressure suppressor (eg trichloroethane or dichloromethane), the amount of suppressor is included as part of the propellant for weight percent calculations. The amount of propellant used is determined by normal factors well known in the art of aerosol. For musses, the propellant level is generally up to 30%, in one aspect from 2% to 30%, in another aspect is from 3% to 15% by weight, in another additional aspect based on the total weight of the composition, if a propellant such as dimethyl ether includes a vapor pressure suppressor (e.g. trichloroethane or dichloromethane), for weight percent calculations, the amount of suppressor is included as part of the propellant.

Examples of perpetual materials include, but are not limited to, titanium dioxide coated mica, iron oxide coated mica, ethylene glycol monostearate, ethylene glycol distearate, polyethylene glycol distearate, bismuth oxychloride, coated mica, myristyl myristate, guanine, glitter (polyester or metallic), and mixtures thereof.

Other perpetual materials can be found in U.S. Patent

No. 4,654,207 and U.S. Patent 5,019,376, incorporated herein by reference. The amount of the beading material may generally be used in amounts from about 0.05% to about 10% and desirably from about 0.15% to about 3% by weight based on the total weight of the stabilized composition.

Examples of insoluble compounds include, but are not limited to, titanium dioxide; pumice; calcium carbonate; baby powder; potato starch; tapioca starch; jojoba pearls; polyethylene beads; nut shells; Luffcr sponge, apricot seeds; almond flour; cornflour; paraffin; oat bran / oat shells; gelatin beads; alginate beads; stainless steel fibers; iron oxide pigments; air bubbles; iron oxide coated membranes; kaolin clay; zinc pyrithione; salicylic acid; zinc oxide; zeolite; polystyrene foam beads; phosphates; silica, and the like. Other generally insoluble compounds include tea tree powder, microspheres, Confetti (a trademark of the United Guardian Company), talc, beeswax, and the like. The amount of insoluble compounds incorporated in the present compositions will vary depending upon their purpose, desired end result, and effectiveness thereof. Therefore, amounts may vary widely, but will often be in the general range of from about 0.1% to about 50% by weight based on the total weight of the composition. A diluent such as water (often deionized) may be used and typically comprises from about 5 wt% to about 99 wt%, and preferably from about 20 wt% to about 99 wt%. total weight of the personal care compositions of the present invention.

Advantageous skin and / or hair conditioners include allantoin; pyrrolidone carboxylic acid and its salts; hyaluronic acid and its salts; sorbic acid and its salts; urea; lysine, arginine, cystine, guanidine, and other amino acids; polyhydroxy alcohols, such as glycerine, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, hexylene glycol, hexanotriol, ethoxydiglycol, dimethicone copolyols, sorbitol, mannitol, xylitol, tripropylene glycol, tetrapropylene glycol, butylene glycol, 1, 3-butylene glycol, 1,3-propanediol, 2,4-dihydroxy-2-methylpentane, and the esters thereof; polyethylene glycol; glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (eg ammonium and quaternary alkyl ammonium); sugars and starches; sugar and starch derivatives (e.g. alkoxylated glucose); panthenols, such as di-panthenol; lactamide monoethanolamine; acetamide monoethanolamine; and analogs, and mixtures thereof.

Said advantageous humectants typically comprise from about 1 wt% to about 10 wt%, preferably from about 2 wt% to about 8 wt%, and more preferably from about 3 wt% to about 5% by weight of the total weight of the personal care compositions of the present invention.

Advantageous lubricants and slip aids include volatile silicones, such as cyclic and linear polydimethylsiloxanes, and the like. The number of silicon atoms in cyclic silicones is preferably from about 3 to about 7, and more preferably 4 or 5. Exemplary cyclic as well as linear volatile silicones are available from Dow Corning Corporation as Dow Corning fluids 344, 345 and 200; Union Carbide as Silicone 7202 and Silicone 7158; and from Stauffer Chemical as SWS-03314.

Volatile linear silicones typically have viscosities of less than about 5 mPa s at 25 ° C, while volatile cyclic silicones typically have viscosities of less than about 10 mPa s at 25 ° C. "Volatile" means that silicone has a measurable vapor pressure. A description of volatile silicones can be found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, vol. 91, pp. 29-32, 1976 incorporated herein by reference. Other advantageous lubricants include polydimethylsiloxane gums, aminosilicones, phenylsilicones, polydimethyl siloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane gums, polyphenyl methyl siloxane gums, amodimethicone, trimethylsiloxaminesilane dimethylamines, dimethylaminesilone dimethylamines, dimethylsiloxane. It is also possible to use lubricant blends. Advantageous lubricants typically comprise from about 0.10 wt% to about 15 wt%, preferably from about 0.1 wt% to about 10 wt%, and more preferably from about 0 wt%. 0.5 wt.% To about 5 wt.% Of the total weight of the personal care compositions of the present invention.

Optionally, compositions of the present invention may include an emollient selected from silicone fluids (e.g., volatile silicone oils and nonvolatile silicone oils); mineral oils; petrolatums; vegetable oils; hydrogenated vegetable oils; fish oils; fatty alcohols; fatty acids; fatty acid and fatty alcohol esters; alkoxylated fatty alcohols; alkoxylated fatty acid esters; benzoate esters; Guerbet esters; alkyl ether polyethylene glycol derivatives, such as, for example, methoxypolyethylene glycol (MPEG); and polyalkylene glycols; lanolin and lanolin derivatives; waxes; and analogs. The emollient may be used alone or in combination with one or more emollients of the present invention. The emollient (s) may be used in an amount comprising from about 0.5 wt% to about 50 wt% of the total antiperspirant composition in a 0.1 wt% to 25 wt% aspect. by weight in another aspect, and from 5% by weight to 40% by weight in another additional aspect. Volatile silicone oils include cyclic and linear polydimethylsiloxanes, low molecular weight organo-functional silicones, and the like. Volatile cyclic silicones (cyclomethicones) typically contain about 3 to about 7 silicon atoms, alternating with oxygen atoms, in a cyclic ring structure. Each silicon atom is typically substituted by two alkyl groups, such as methyl groups.

Volatile linear polydimethylsiloxanes (dimethicones) typically contain from about 2 to about 9 silicon atoms, alternating with oxygen atoms in a linear arrangement. Each silicon atom is also substituted by two alkyl groups (the terminal silicon atoms are replaced by three alkyl groups), such as methyl groups. Volatile linear silicones typically have viscosities of less than about 5 cP at 25 ° C, while volatile cyclic silicones typically have viscosities of less than about 10 cP at 25 ° C. "Volatile" means that silicone has a measurable vapor pressure, or a vapor pressure of at least 2 mm Hg at 20 ° C. Nonvolatile silicones have a vapor pressure of less than 2 mm Hg at 20 ° C. A description of volatile silicones is found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, vol. 91, pp. 29-32, 1976, and in Kasprzak, "Volatile silicones", Soap / Cosmetics / Chemical Specialties, p. 40-43, December 1986, each of which is incorporated herein by reference.

Exemplary volatile cyclomethicones are cyclomethicone D4 (octamethylcyclotetrasiloxane), cyclomethicone D5 (decamethylcyclopentasiloxane), cyclomethicone D6, and mixtures thereof (e.g., D4 / D5 and D5 / D6). Volatile cyclomethicones and cyclomethicone mixtures are commercially obtainable from G. E. Silicones such as SF1173, SF1202, SF1256, and SF1258, Dow Corning Corporation as Dow Corning® 244, 245, 246, 345, and 1401 Fluids. Combinations of volatile cyclomethicones and volatile linear dimethicones are also considered.

Exemplary volatile linear dimethicones include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and combinations thereof, volatile linear dimethicones and dimethicone combinations are commercially available from Dow Corning Corporation as Dow Corning 200® Fluid (e.g. CST, 1 CST, 1.5 CST, and 2 CST) and Dow Corning® 2-1184 Fluid.

Exemplary volatile low molecular weight organo-functional silicones include phenyl trimethicone, caprylyl trimethicone, caprylyl methicone, and hexyl methicone, and combinations thereof, low molecular weight organo-functional silicones are commercially available from Clariant under the tradename Silcare® 41M10 , Slicare® 31M60, Silcare® 41 M 10, and Silcare® 41 M 15.

Non-volatile silicone oils useful as emollients in the present invention are linear and typically have viscosities of from about 10 cP to about 100,000 cP at 25 ° C. They typically contain more than about 10 dialkyl / diaryl or monoalkyl / monoaryl-substituted silicon atoms, alternating with oxygen atoms in a linear arrangement. They include polyalkylsiloxane polymers, polyarylsiloxane, and polyalkylarylsiloxane. Exemplary nonvolatile silicone oils include polydimethylsiloxanes (dimethicones), polydiethylsiloxanes, polymethylphenylsiloxanes, and the like. In one aspect of the invention, nonvolatile silicone oil is selected from a nonvolatile polydimethylsiloxane having a viscosity range from about 10 cP to about 100,000 cP at 25 ° C. Nonvolatile dimethicones are commercially available from Dow Corning Corporation as Dow Corning 200® Fluid (product names 10 CST to 10,000 CST). Mineral oils and petrolatums include cosmetic grades, USP and NF and are commercially available from Penreco under the trade names Drakeol® and Penreco®. Advantageous exemplary vegetable oils as an emollient component in the present invention include, but are not limited to, peanut oil, sesame oil, avocado oil, coconut oil, cocoa butter, almond oil, saffron oil, corn oil, oil. cottonseed, castor oil, olive oil, jojoba oil, palm oil, palm heart oil, soybean oil, wheat germ oil, flaxseed oil, sunflower seed oil; and the mono-, di-, and triglycerides thereof, and hydrogenated derivatives thereof; and mixtures thereof. Exemplary mono-, di- and triglycerides are, for example, caprylic triglyceride, capric triglyceride, caprylic / capric triglyceride, and caprylic / capric / lauric triglyceride, caprylic / capric / stearic triglyceride, and caprylic / capric / linoleic triglyceride.

Ethoxylated mono- and diglycerides of the foregoing vegetable oils are also considered to fall within the scope of the present invention, such as, for example, PEG-8 caprylic / capric glycerides.

Advantageous fatty alcohol softeners include, but are not limited to, fatty alcohols containing from 8 to 50 carbon atoms. Exemplary fatty alcohols include capryl alcohol, pelargonic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, ricinoleyl alcohol, arachidyl alcohol, icocenyl alcohol, beenyl alcohol, and mixtures thereof.

Advantageous fatty acid softeners include, but are not limited to, fatty acids containing from 10 to 50 carbon atoms. Exemplary fatty acids are selected from capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, and mixtures thereof.

Advantageous fatty alcohol and fatty acid ester emollients include, but are not limited to, hexyl laurate, decyl oleate, isopropyl stearate, isopropyl isostearate, butyl stearate, cetyl stearate, myristyl myristate, stearoilstearate octyldodecyl, octyl hydroxystearate, diisopropyl adipate, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, isodecyl oleate, diisopropyl sebaceate, isostearyl lactate, isostearyl lactate estearate dihydrate diethyl hexyl maleate, PPG-14 butyl ether and PPG-2 myristyl ether propionate, ethylhexyl octanoate, cetearyl octanoate, and mixtures thereof. Alkoxylated fatty alcohols are ethers formed from the reaction of a fatty alcohol with an alkylene oxide, usually ethylene oxide or propylene oxide. Advantageous ethoxylated fatty alcohols are chemical addition products of fatty alcohols and polyethylene oxide. In one aspect of the invention the ethoxylated fatty alcohols may be represented by the formula R- (OCH2CH2) n-OH wherein R represents the linear or branched aliphatic radical of the parent fatty alcohol and n represents the number of ethylene oxide molecules. In another aspect of the invention, R is derived from a fatty alcohol containing from 8 to 40 carbon atoms. In one aspect n is an integer comprising from 2 to 100, from 3 to 80 in another aspect, and from 3 to 50 in another additional aspect. In a further aspect, R is derived from a fatty alcohol softener presented above. Exemplary ethoxylated fatty alcohols include, but are not limited to, capryl alcohol ethoxylate, lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate ethoxylated ethoxyl alcohol ethoxylate , and beenyl alcohol ethoxylate, the number of ethylene oxide units in each of the preceding ethoxylates may comprise from 2 and above in one aspect and from 2 to about 150 in another aspect. It should be recognized that propoxylated fatty acid chemical adducts and ethoxylated / propoxylated chemical adducts of the preceding fatty alcohols are also considered to fall within the scope of the invention. More specific examples of alkoxylated alcohols are beenet 5-30 (with 5-30 being the number of repetitive ethylene oxide or propylene oxide units), Cetearet 2-100, Ceteth 1-45, Cetolet 24-25, Cholet 10 -24, Cocet 3-10, C9-11 Paret 3-8, Cl 1-15 paret 5-40, Cl 1-21 Paret 3-10, C12-13 Paret 3-15, Decet 4-6, Dodoxynol 5- 12, Glyceret 7-26, Isocetet 10-30, Isodecet 4-6, Isolauret 3-6, Isostearet 3-50, Lanet 5-75, Lauret 1-40, Nonoxynol 1-120, Nonoxynol 5-150, Octoxinol 3- 70, Olet 2-50, Stearet 2-100, Tridecet 2-10, and so on. Alkoxylated fatty acids are formed when a fatty acid is reacted with an alkylene oxide or a preformed polymer ether. The resulting product may be a monoester, diester, or mixture thereof. Advantageous ethoxylated fatty acid ester emollients that are suitable for use in the present invention are products of the addition of ethylene oxide to fatty acids. The product is a fatty acid polyethylene oxide ester. In one aspect of the invention, ethoxylated fatty acid esters may be represented by the formula RC (O) 0 (CH 2 CH 20) n H, where R represents the linear or branched aliphatic radical of a fatty acid and n represents the number of oxide molecules of ethylene. In another aspect, n is an integer comprising from 2 to 50, from 3 to 25 in another aspect, and from 3 to 10 in another additional aspect. In another further aspect of the invention, R is derived from a fat containing from 8 to 30 carbon atoms.

In a further aspect, R is derived from a fatty acid softener set forth above. It should be recognized that propoxylated and ethoxylated / propoxylated products of the preceding fatty acids are also considered to fall within the scope of the invention. Exemplary alkoxylated fatty acid esters include, but are not limited to, capric acid ethoxylate, lauric acid ethoxylate, myristic ethoxylate, stearic acid ethoxylate, coconut fatty acid ethoxylate, and polyoxypropylene glycol propylate 400 monolaurate wherein the number of ethylene oxide units in each of the preceding ethoxylates may comprise from 2 and more in one aspect, and from 2 to about 50 in another aspect. More specific examples of ethoxylated fatty acids are PEG-8 distearate (with 8 being the number of repeating units of ethylene oxide), PEG-8 beenate, PEG-8 caprate, PEG-8 caprylate, / PEG-8 caprate, PEG cocoates (PEG without a designation number means the number of ethylene oxide units comprises from 2 to 50), PEG-15 dicocoate, PEG-2 diisononanoate, PEG-8 diisostearate , PEG dilaurates, PEG dioleates PEG distearates, PEG ditalates, PEG isostearates, jojoba-PEG acids, PEG laurates, PEG myristates, PEG oleates, PEG palmitates, PEG ricinolates, PEG stearates, PEG talates, and the like.

Benzoate ester softeners are selected from but not limited to C12 to C15 alkyl benzoate, isostearyl benzoate, octyl dodecyl benzoate, stearyl benzoate, dipropylene glycol dibenzoate, methyl gluczo-20, castor oil benzoate , cetyl ricinoleate benzoate, ethylhexyl hydroxystearate benzoate, dimethicone PEG / PPG-20/23 benzoate, and dimethicone PEG-8 benzoate.

Guerbet ester softeners are formed from an esterification reaction of a Guerbef alcohol with a carboxylic acid.

Guerbet ester emollients are commercially available from Noveon, Inc. as G-20, G-36, G-38, and G-66.

Lanolin and lanolin derivatives are selected from lanolin, lanolin wax, lanolin oil, lanolin alcohols, lanolin fatty acids, alkoxylated lanolin, isopropyl lanolate, acetylated lanolin alcohols, and combinations thereof. Lanolin and lanolin derivatives are commercially available from Noveon, Inc. under the following trade names Lanolin LP 108 USP, Lanolin USP AAA, Acetulan ™, Ceralan ™, Lanocerin ™, Lanogel ™ (product names 21 and 41), Lanogene ™ , Modulan ™, Ohlan ™, Solulan ™ (product names 16, 75, L-575, 98, and C-24), Vilvanolin ™ (product names C, CAB, L-101, and P).

Waxes include those derived from plant, animal / insect, mineral, petroleum, and synthetic sources. Synthetically modified natural waxes (plant and animal / insect) are also considered to fall within the scope of the invention. Exemplary plant-derived waxes include, but are not limited to, laurel berry wax, candelilla wax, hydrolysed candelilla wax, carnauba wax, ethoxylated carnauba wax (e.g. PEG-12 carnauba wax), hydrolyzed carnauba wax, carnauba acid wax, hydrogenated castor wax, esparto wax, hydrogenated Japanese wax, hydrogenated jojoba oil, jojoba oil esters, sulfurized jojoba oil, ouricuri wax, palm heart wax, and wax of hydrogenated rice bran. Exemplary animal / insect waxes include, but are not limited to, beeswax, oxidized beeswax, ethoxylated beeswax (eg, PEG-6 beeswax, PEG-8 beeswax, PEG beeswax). -12, beeswax PEG-20), dimethicone copolyol beeswax esters and dimethiconol beeswax ester (eg bishydroxyethoxypropyl dimethicone beeswax esters, PEG-dimethicone beeswax 8, and dimethiconol beeswax obtainable from Noveon, Inc. under the tradename Ultrabee®), Chinese wax, shellac wax, spermacet wax, mink wax, and lanolin wax.

Exemplary mineral waxes include, but are not limited to, ceresine waxes, montana wax, montana acid wax, and ozocerite. Exemplary petroleum waxes include paraffin waxes, microcrystalline waxes, and oxidized microcrystalline waxes. Exemplary synthetic waxes include synthetic beeswax, synthetic candelilla wax, synthetic carnauba wax, synthetic japanese wax, synthetic jojoba oil, polyolefin waxes (eg, polyethylene wax), ethylene glycol diesters or acid triesters. fatty acids containing from 18 to 40 carbon atoms. Mixtures of two or more of the preceding waxes and wax classes are also considered. Various antiperspirant agents that may be used in accordance with the present invention include conventional antiperspirant metal salts and metal salt complexes. In one aspect of the invention the metal salts and metal salt complexes used as antiperspirant agents are acidic and are based on aluminum and zirconium and combinations thereof. These salts include, but are not limited to, aluminum halides, aluminum hydroxy halides, aluminum sulfate, zirconium (zirconyl) oxide halides, zirconium (zirconyl) hydroxy halides, and mixtures or complexes thereof. Aluminum and zirconium salt complexes include amino acid and aluminum zirconium salt complexes such as glycine or glycol complexes such as propylene glycol (PG) or polyethylene glycol (PEG).

Exemplary antiperspirant agents include, but are not limited to, aluminum chloride, aluminum hydrochloride, aluminum dihydrochloride, aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum chloridrex PEG (aluminum chloridrex aluminum polypropylene) glycol), aluminum dichloridrex PEG (aluminum dichloridrex polyethylene glycol), aluminum dichloridrex PG (aluminum dichloridrex propylene glycol), aluminum sesquichloridrex PEG (aluminum sesquichloridrex aluminum propylene glycol) sesquichloridrex aluminum propylene glycol) , aluminum zirconium trihydrochloride, aluminum zirconium tetrahydrochloride, aluminum zirconium penthydrochloride, aluminum zirconium octochloride, aluminum zirconium chloride hydrochloride (aluminum zirconium chloride hydrochloride), aluminum zirconium trichloride hydroxide GLY (aluminum zirconium trichloride hydrochloride) GLY aluminum zirconium (aluminum zirconium tetrachloridrex glycine), GLY aluminum zirconium pentachloridrex (aluminum zirconium pentachloridrex glycine), and GLY aluminum zirconium octachloridrex glycine (aluminum zirconium octachloridrex glycine). Other antiperspirant agents include ferric chloride and zirconium powder. Mixtures of any of the foregoing antiperspirant agents are also advantageous for use in the present invention. The amount of antiperspirant incorporated into the compositions of the present invention is an amount that is sufficient to reduce the perspiration flow from a location where the antiperspirant is applied, for example to the axillary area of the human body.

Generally, the level of antiperspirant used in the compositions of the present invention comprises from about 0.5 wt% to about 35 wt% based on the total weight of the composition. In another aspect of the invention, the amount of antiperspirant in the composition may comprise from about 5 wt% to about 25 wt%, in a further aspect from about 5 wt% to about 20 wt%, and in an additional aspect from about 10 wt% to about 15 wt%, based on the total weight of the composition. The foregoing weight percentages are calculated on an anhydrous metal salt base solely on the complexing agent (e.g., glycine or glycol).

Advantageous neutralizers include triethanolamine, aminomethyl propanol, ammonium hydroxide, sodium hydroxide, other alkaline hydroxides, borates, phosphates, pyrophosphates, cocamine, oleamine, diisopropanolamine, diisopropylamine, dodecylamine, PEG-15 cocamine, morpholine, tetraamylamethylamethylamine (triethylamine) triethanolamine, triethylamine, 2-amino-2- (hydroxymethyl) -1,3-propanediol tromethamine, and the like, and mixtures thereof. Advantageous neutralizers typically comprise from about 0 wt% to about 3 wt%, preferably from about 0.01 wt% to about 2 wt%, and more preferably from about 0.1 wt%. % by weight to about 1% by weight of the total weight of the personal care compositions of the present invention. The foregoing neutralizers may be employed to neutralize the polymer or adjust the pH of the final formulated composition.

Advantageous opacifiers include glycol fatty acid esters; alkoxylated fatty acid esters; fatty acid alcohols; hydrogenated fatty acids, polymeric opacifiers, waxes and oils; kaolin; magnesium silicate; titanium dioxide; silica; and analogs, and mixtures thereof. Advantageous opacifiers typically comprise from about 0.1 wt% to about 8 wt%, preferably from about 0.5 wt% to about 6 wt%, and more preferably from about 1 wt%. % by weight to about 5% by weight of the total weight of the personal care compositions of the present invention.

Advantageous pharmaceutical actives useful in the present invention include any advantageous chemical, material or compound for topical administration to induce any desired local or systemic effect.

Active ingredients include, but are not limited to, antibiotics, antiviral agents, analgesics (eg ibuprofen, acetyl salicylic acid, naproxen, and the like), antihistamines, anti-inflammatory agents, antipruritics, antipyretics, anesthetic agents, diagnostic agents, hormones, antifungals, antimicrobials, anti-dandruff, skin growth enhancers, pigment modulators, antiproliferatives, antipsoriatics, retinoids, anti-acne drugs (eg benzoyl peroxide, sulfur, and the like), antineoplastic agents, phototherapeutic agents, and quertolysis (p. resorcinol, salicylic acid, and the like), botanical extracts, and the like, and mixtures thereof. Botanical extracts are commercially available from Cosmetochem International Ltd., Steinhausen, Switzerland. Such pharmaceutical actives typically comprise from about 0.1 wt% to about 20 wt% of the total weight of the personal care compositions of the present invention.

Advantageous preservatives include bicyclic polymethoxy oxazolidine, methyl paraben, propyl paraben, ethyl paraben, butyl paraben, benzoic acid and benzoic acid salts, e.g. e.g. sodium benzoate, benzalkonium chloride, benzyltriazole, DMDM hydantoin (also known as 1,3-dimethyl-5,5-dimethyl hydantoin), iodopropynyl butylcarbonate, imidazolidinyl urea, phenoxyethanol, phenoxyethylparaben, methylisothiazolinone, methylchloroisothiazolinone, benzoate sorbic acid, salicylic acid salts, and the like, and mixtures thereof. Said advantageous preservatives typically comprise from about 0.01 wt.% To about 1.5 wt.%, Preferably from about 0.1 wt.% To about 1 wt.%, And more preferably from about 0.01 wt.%. from 0.3 wt% to about 1 wt% of the total weight of the personal care compositions of the present invention.

Advantageous spreading aids or sliding aids include hydroxypropyl methylcellulose, hydrophobically modified cellulosics, xanthan gum, cassia gum, guar gum, carob pod gum, dimethicone copolols of varying degrees of alkali, boron nitride, talc, and the like, and mixtures of the same. Said spreading aids or advantageous sliding aids typically comprise from about 0.01 wt% to about 5 wt%, preferably from about 0.1 wt% to about 3 wt%, and more. preferably from about 0.1 wt% to about 2.0 wt% of the total weight of the personal care compositions of the present invention.

Advantageous sunscreens may be used in safe and photoprotectively effective amounts in the personal care compositions of the present invention. Advantageous sunscreens include those presented in Segarin et al., "Cosmetics Science and Technology," Chapter VIII, pages 1890 ff., And also in 64 Federal Register, vol. 64, No.98, pp. 27666-27693, May 21, 1999. Advantageous specific sunscreen agents include, for example, p-aminobenzoic acid and its salts and derivatives (ethyl, isobutyl, glyceryl esters; p-dimethylaminobenzoic acid; 2-ethylexyl-N, N-dimethylaminobenzoate); anthranilates (i.e., o-aminobenzoates; methyl, octyl, amyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, and cyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl, menthyl, glyceryl, and dipropylene glycol esters); cinnamic acid derivatives (ethylexyl-p-methoxy; benzyl menthyl esters, phenyl cinnamonitrile; butyl cinnamoyl pyruvate); cinnamic dihydroxy acid derivatives (umbeliferone, methylumbeliferone, methylaceto-umbeliferone); cinnamic trihydroxy acid derivatives (esculetin, methylsculetin, daffnetin, and glucosides, esculin and daffin); hydrocarbons (diphenylbutadiene, stilbene); dibenzalacetone and benzalacetophenone; naphthol sulfonates (sodium salts of 2-naphthol-3,6-disulfonic acid and 2-naphthol-6,8-disulfonic acid); dihydroxy naphthoic acid and its salts; o- and p-hydroxybiphenyldisulfonates; coumarin derivatives (7-hydroxy, 7-methyl, 3-phenyl); diazols (2-acetyl-3-bromoindazole, phenyl benzoxazole, methyl naphthoxazole, various aryl benzothiazoles); quinine salts (bisulfate, sulfate, chloride, oleate, and tanate); quinoline derivatives (8-hydroxyquinoline, 2-phenyl quinoline salts); hydroxymethoxy substituted benzophenones; uric and villuric acid; tannic acid and its derivatives (e.g. hexaethyl ether); (butyl carbityl) (6-propyl piperonyl) ether; hydroquinone; benzophenones (oxybenzone, sulisobenzone, dioxibenzone, benzoresorcinol, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, octabenzone; 4-isopropylbenzoylmethane; butylmethoxybenzylmethane; isopropylene; dibenzoylmethane, and camphor derivatives such as methylbenzylidene or benzylidene camphor and the like, and mixtures thereof Other sunscreens include inorganic sunscreens such as titanium dioxide (micronized titanium dioxide, 0.03 microns), zinc oxide , silica, iron oxide and dioxide, and the like, and mixtures thereof and with the previously indicated organic sunscreens Without wishing to be bound by theory, it is believed that these inorganic materials provide a benefit of reflection solar filtration , diffraction, and absorption of harmful visible and infrared UV radiation.Ethylexyl p-methoxycinnamate, octyl salicylate, and ben zofenone, either alone, as a mixture, or in combination with titanium dioxide [which works] as a physical sunscreen.

By "safely and photoprotectively" is meant an amount of sunscreen sufficient to provide photoprotection when the composition is applied, but not so much as to cause any side effects such as skin reactions. Advantageous sunscreens typically comprise from about 0.5 wt% to about 50 wt%, preferably from about 0.5 wt% to about 30 wt%, and more preferably from about 0 wt%. 0.5 wt.% To about 20 wt.% Of the total weight of the skin and hair care compositions of the present invention. Exact amounts will vary depending on the sunscreen selected and the desired Sun Protection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen against erythema. This number is derived from another parameter, the minimum erythemal dose (MED). MED is defined as the lowest exposure dose at a specified wavelength that will elicit a delayed erythema response. MED indicates the amount of energy reaching the skin and the skin's responsiveness to radiation. SPF (sun protection factor) is obtained by dividing the MED of the skin protected by the MED of the unprotected skin. The higher the SPF, the more effective is the agent in preventing sunburn. The SPF value indicates how many times longer a person can stay in the sun with sunscreen (compared to the same person with unprotected skin) before the person experiences 1 MED. For example, using a sunscreen with an SPF of 6 will allow the individual to stay in the sun for six times longer before receiving MED. As the SPF value of a sunscreen rises, there is less chance of developing tanning of the skin. Commercially obtainable sunscreen products have FPBS values ranging from 2 to 50.

Advantageous viscosity adjusting agents or diluents include isopropyl alcohol, ethanol, sorbitol, propylene glycol, diethylene glycol, triethylene glycol, dimethyl ether, butylene glycol, and the like, and mixtures thereof. Said viscosity adjusters or advantageous diluents typically comprise from about 0.1 wt% to about 85 wt% in one aspect, from about 1 wt% to about 60 wt% in another aspect and about 5 wt% to about 40 wt% in an additional aspect of the total weight of the personal care compositions of the present invention.

Skin conditioning polymers include quaternized guar gum, quaternized cellulose, polyquatemium 4, polyquatemium 7, polyquatemium 10, polyquatemium 11, polyquatemium 39, polyquatemium 44, and the like, and mixtures thereof. Said advantageous conditioning agents typically comprise from about 0.01 wt% to about 5 wt%, preferably from about 0.1 wt% to about 3 wt%, and more preferably from about 0.01 wt%. 0.1 wt.% To about 2 wt.% Of the total weight of the skin care compositions of the present invention. Various vitamins may also be included in the compositions of the present invention. Advantageous vitamins include, but are not limited to, vitamin A, vitamin B, biotin, pantothenic acid, vitamin C, vitamin D, vitamin E, tocopherol acetate, retinyl palmitate, ascorbyl magnesium phosphate, and the like, and derivatives and mixtures thereof. .

Advantageous rheology / emulsifier modifiers and texture modifiers include natural, semi-synthetic, and synthetic polymers. Examples of modified natural and natural polymers include polygalactomannan gums and modified polygalactomannan gums such as guar gum and cassia gum, xanthan gums, cellulosics, modified cellulosics, starches, polysaccharides, and the like. Modified pligalactomannan gums and modified polygalactomannan gums are disclosed in U.S. Patent 4,753,659 and International Patent Application Nos. WO2004 / 113390 and WO2004 / 112733. Examples of synthetic polymers include polyalylaccharose cross-linked acrylic acid polymers and copolymers as described in US Patent 2,798,053 which is incorporated herein by reference, polyacrylates, acrylate copolymers or intumescible alkaline emulsion acrylate copolymers (e.g., Aculyn® 33 , Rohm and Haas;

Carbopol® Aqua SF-1, Noveon, Inc.), hydrophobically modified alkaline swellable copolymers (e.g., Aculyn 22, Aculyn 28 and Aculyn 38, Rohm and Haas), hydrophobically modified nonionic polyurethanes (e.g. Aculyn 44, Rohm and Haas), polyethylene oxides (e.g., PEG-90M and PEG-180M, Dow / Amerchol Polyox ™ resins), and the like.

Commercially obtainable crosslinked acrylic acid homopolymers include Carbopol® 934, 940, 941, 956, 980, and 996 carbomers obtainable from Noveon, Inc. Other commercially obtainable crosslinked acrylic acid copolymer rheology modifiers include the Carbopol® Ultrez (Ultrez class) series. 10, 20 and 21) and the rheology modifiers of the ETD class series (ETD 2020 and 2050) obtainable from Noveon, Inc. It is also possible to use mixtures of the preceding natural, modified natural and synthetic polymers. Said advantageous rheology modifiers / emulsifiers, alone or in combination, typically comprise from about 0.1 wt% to about 5 wt%, preferably from about 0.3 wt% to about 3 wt% and most preferably from about 0.5 wt% to about 2 wt% of the total weight of the personal care compositions of the present invention.

The polymers of the present invention which are prepared as aqueous emulsions are particularly useful for water-based formulations, and are not limited to, but not limited to, water dilutants or auxiliary solvents. Commonly employed useful solvents are typically liquids such as water (deionized, distilled or purified), alcohols, fatty alcohols, polyols, and the like, and mixtures thereof. Non-aqueous or hydrophobic auxiliary solvents are commonly employed in substantially water-free products such as nail polishes, aerosol-propelling sprays, or for specific functions such as removing oily dirt, tallow, makeup, or dissolving dyes, fragrances, and analogues, or are incorporated into the oil phase of an emulsion. Non-limiting examples of auxiliary solvents, other than water, include straight and branched alcohols, such as ethanol, propanol, isopropanol, hexanol, and the like; aromatic alcohols, such as benzyl alcohol, cyclohexanol, and the like; fatty alcohol saturated with from C12 to C30, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, beenyl alcohol, and the like. Non-limiting examples of polyols include polyhydroxy alcohols such as glycerine, propylene glycol, butylene glycol, hexylene glycol, C2 to C4 alkoxylated alcohols and C2 to C4 alkoxylated polyols such as ethoxylated, propoxylated ethers, and butoxylated alcohols, diols and polyols having from about 2 to about 30 carbon atoms and from 1 to about 40 alkoxy units, polypropylene glycol, polybutylene glycol, and the like. Non-limiting examples of non-aqueous auxiliary diluents or solvents include silicones, and silicone derivatives such as cyclomethicone, and analogs, ketones such as acetone and methylethyl ketone; waxes of natural and synthetic oils, such as vegetable oils, vegetable oils, animal oils, essential oils, mineral oils, C7 to C40 isoparaffins, alkyl carboxylic esters such as ethyl acetate, amyl acetate, ethyl lactate, and the like, jojoba oil, shark liver oil, and the like. Some of the foregoing non-aqueous auxiliary diluents or solvents may also be conditioners and emulsifiers.

Surfactants are generally employed as cleansing agents, emulsifying agents, stabilizers, foam enhancers, structuring, hydrotropic and suspending agents. The copolyol dimethicone polymers of the present invention may be employed in formulations containing all classes of surfactants, i.e. anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants. The term "amphoteric surfactant" as used herein includes zwitterionic surfactants. In addition to the foregoing references, surfactant class discussions can be found in "Cosmetics & Toiletries® C&T

Ingredient Resource Series, "Surfactant Encyclopedia", 2nd edition, Rieger (ed), Allured Publishing Corporation (1996); Schwartz, et al, "Surface Active Agents, Their Chemistry and Technology," published in 1949; and "Surface Active Agents and Detergents", Volume II, published in 1958, Interscience Publishers; each incorporated herein by reference.

Anionic surfactants include substances having a negatively charged hydrophobic or carrying a negative charge when the pH is raised to or above neutrality, such as acylamino acids, and salts thereof, for example acylglutamates, acyl peptides, sarcosinates, and taurates; carboxylic acids, and salts thereof, for example alkanolic acids and alkanoates, carboxylic ester acids, and carboxylic ether acids; phosphoric acid ester and salts thereof; sulfonic acids and salts thereof, for example, acyl isethionates, alkylaryl sulfonates, alkyl sulfonates, and sulfosuccinates; and sulfuric acid esters such as alkyl ether sulfates and alkyl sulfates.

Nonlimiting examples of anionic surfactants include mono-basic salts of acylglutamates which are slightly acidic in aqueous solution, such as sodium acylglutamate and sodium hydrogenated talol glutamate; salts of acyl hydrolyzed protein such as potassium, palmitoyl hydrolyzed milk protein, sodium cocoa hydrolyzed soy protein, and TEA-abietoyl hydrolyzed collagen; acyl sarcosinate salts such as ammonium myristoyl sarcosine, sodium cocoyl sarcosinate, and lauroyl TEA-sarcosinate; sodium methyl acyltaurate salts, such as sodium lauroyl taurate, sodium methyl oleyl taurate and sodium methyl cocoyl taurate; alkanoic acids and alkanoates, such as fatty acids derived from animal and vegetable glycerides that form water-soluble soaps and water-insoluble emulsifying soaps, including sodium stearate, ammonium stearate, aluminum stearate, and zinc undecylenate; carboxylic ester acids such as dinonoxynol-9-citrate; acyl lactylate salts such as calcium stearoyl lactylate and lauret-6 citrate; ether carboxylic acids derived from ethoxylated alcohols or phenols having varying lengths of polyoxyethylene chains, such as nonoxynol-8 carboxylic acid, and sodium tridecet-13 carboxylate; phosphoric acid mono-and di-esters and their salts, such as phospholipids, dilauret-4-phosphate, DEA-olet-10 phosphate and triethanolamine lauryl phosphate; acylisethionate salts, such as sodium cocoyl isethionate; alkylarylbenzene sulfonates, such as alpha olefin (AOS) and alkali metal sulfonates, alkaline earth metal, and alkanolamine salts thereof, and sodium dodecylbenzene sulfonate; alkyl sulfonates such as C12 to C14 sodium olefin sulfonate, C14 to C16 sodium olefin sulfonate, sodium cocomonoglyceride sulfonate, C12 to C15 sodium parethan sulfonate, and C12 to C15 lauryl sulfonate. sodium; sulfosuccinates, such as sulfosuccinic acid mono and diesters, salts thereof and alkylamido and alkoxylated alkyl derivatives thereof, such as C4 to C10 di-alkyl sodium sulfosuccinate, disodium lauret disodium oleamide MEA-sulfosuccinate, and paret disodium sulfoscincinate having from C 12 to C 15; alkyl ether sulfates, such as sodium lauryl ether and ammonium sulfate (having from about 1 to about 12 moles of ethylene oxide), e.g. e.g. sodium lauret sulfate; alkyl sulfates, such as sodium, ammonium and triethanolamine salts of C1-2 to C1-8 alkylsulfates, sodium C1-2 to C4 olefin sulfates, sodium lauret-6 carboxylate, C12 to C12 sodium paretulfate, and the like .

Cationic surfactants may have a hydrophobic that carries a positive charge or is uncharged at or near neutral pH values, such as alkylamines, alkyl imidazolines, ethoxylated amines, and quaternary ammonium compounds. Cationic surfactants used in cosmetics are preferably N-derivatives and the neutralizing anion may be inorganic or organic. Among the cationic surfactant materials useful herein are quaternary ammonium compounds corresponding to the general formula: (R 1 R 2 R 4 R 17 R) E, each of which R 14, R 15, R 16, and R 17 are independently selected from a group. aliphatic having from 1 to about 30 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having from 1 to about 22 carbon atoms in the alkyl chain; and E is a salt-forming anion, such as those selected from halogen, (eg chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether bonds, ester bonds, and other groups, such as amino groups. Longer chain aliphatic groups, e.g. e.g., those of about 12 carbons or more may be saturated or unsaturated.

Alkylamines may be substituted or unsubstituted primary C12 to C22 fatty alkyl salts of C12 to C22, and substances sometimes referred to as "amidoamines". Non-limiting examples of alkyl amines and salts thereof include dimethyl cocamine, dimethyl palmitamine, dioctylamine, dimethyl stearamine, dimethyl soybean, soybean, myristyl amine, tridecyl amine, ethyl stearylamine, N-talolpropane diamine, ethoxylated stearylamine, dihydrylamine aryl, , dimethyl lauramine, stearylamine hydrochloride, soybean chloride, stearylamine formate, N-talolpropane diamine dichloride, and amodimethicone (INCI name for a silicone polymer and blocked with amino functional groups such as aminoethylamino propylsiloxane). Non-limiting examples of amidoamines and salts thereof include propyl dimethyl amine stearamido, stearamidopropyl dimethylamine citrate, palmitamidopropyl diethylamine, and cocamidopropyl dimethylamine lactate. Other cationic surfactants include distearyldimmonium chloride, dikethyldimmonium chloride, guar hydroxypropyltrimmonium chloride, and the like. At low pH, amine oxides may protonate and behave similarly to N-alkyl amines.

Non-limiting examples of alkyl imidazolines include alkyl hydroxyethyl imidazoline such as stearyl hydroxyethyl imidazoline, coconut hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like. Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, PEG-15 talol amine, quaternium-52, and the like.

Quaternary ammonium compounds are monomeric or polymeric materials containing at least one nitrogen atom that is covalently bonded to four alkyl and / or aryl substituents, and the nitrogen atom remains positively charged regardless of ambient pH. Quaternary ammonium compounds comprise a large number of substances that are used extensively as surfactants, conditioners, antistatic agents, and antimicrobial agents and include alkylbenzyldimethyl ammonium salts, alkyl betaines, heterocyclic ammonium salts, and tetraalkylammonium salts. Long chain alkylbenzidylmethyl ammonium (fatty) salts are preferred as conditioners, as antistatic agents, and as fabric softeners, discussed in more detail below. Other quaternary ammonium compounds include quaternary ammonium silicones.

Non-limiting examples of alkylbenzyldimethylammonium salts include stearalkonium chloride, benzalkonium chloride, quaternium-63, olealconium chloride, didecyldimonium chloride, and the like. Alkyl betaine compounds include alkylamidopropyl betaine, alkylamidopropyl hydroxysultaine, and sodium alkyl propyl hydroxyphostaine. Non-limiting examples of alkyl betaine compounds include oleyl betaine, cocaine betaine, cocamidopropyl betaine, cocohydroxy sultaine, coco / oleamidopropyl betaine, coco sultaine, cocoamidopropyl hydroxy sultaine, and sodium lauramidopropyl hydroxyphostaine. Heterocyclic ammonium salts include alkyl ethyl morpholine ethosulfate, isostearyl ethyl imidon ethos sulfate, and alkyl pyridinium chlorides, and are generally used as emulsifying agents.

Nonlimiting examples of heterocyclic ammonium salts include cetylpyridinium chloride, isostearylethylimidonium ethosulfate, and the like. Non-limiting examples of tetraalkylammonium salts include cocamidopropyl ethyldimmonium ethosulfate, hydroxyethyl ketethymmonium chloride, quathemium-18, and hydroxypropyl cocodimonium hydrolyzed protein such as hair keratin, and the like.

Advantageous amphoteric or zwitterionic surfactants for use in the present compositions include those broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, with aliphatic radicals being straight or branched chain, and one of the aliphatic substituents contains about from 8 to about 30 carbon atoms and another substituent contains an anionic group that is solubilized in water, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, and the like. Zwitterionic classes include alkylamino sulfonates, alkyl betaines and alkylamido betaines, such as stearamidopropyldimethylamine, diethylaminoethylstearamide, dimethylstearamine, dimethylsojamine, soybean, myristylamine, tridecylamine, ethylstearylamine ethoxyethylamine ethoxide ethoxylamine ethoxyethylamine ethoxide , arachidylbeenylamine, and the like.

Some advantageous betaine surfactants include, but are not limited to, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkyl amidopropyl hydroxysultins, acyl taurates, and acyl groups have alkyl and acyl groups. 8 to 18 carbon atoms. Nonlimiting examples of preferred amphoteric surfactants include cocamidopropyl betaine, sodium cocoanfoacetate, disodium cocoamphodiacetate, cocamidopropyl hydroxysultaine, and sodium cocoamphopropionate, which are particularly advantageous as mild skin and hair cleansers.

Nonionic surfactants are generally uncharged amphiphiles and are usually alkoxylated to varying degrees. Nonionic surfactant classes include alcohols, alkanolamides, amine oxides, alkyl glucosides, esters, and ethers. Nonionic alcohols are usually hydroxy derivatives of C8 to C18 long chain alkane hydrocarbons, such as cetearyl alcohol, hydrogenated talol alcohol, lanolin alcohols, alkanolamides, and the like. Alcanolamides contain at least one alkoxy or polyoxyethylene group and include alkanol-derived amides such as acylamide DEA, N-alkyl pyrrolidone, palmamide MEA, peanutamide MIPA, and analogs and ethoxylated amides such as PEG-50 talol amide. Amine oxides include alkylamine oxides, such as lauramine oxide; and acylamidopropyl morpholine oxides such as cocamidopropylamine oxide; and analogs. Alkyl glucosides include straight or branched C4 to C24 alkyl glucosides such as nonyl, decyl, dodecyl and lauryl glycosides. Esters include ethoxylated carboxylic acids, such as PEG-8 dilaurate, PEG-8 laurate, and the like; ethoxylated glycerides, such as PEG-4 castor oil, PEG-120 glyceryl stearate, PEG-6 triolein esters, and the like; glycol esters and derivatives thereof, such as SE glycol stearate, propylene glycol ricinoleate, and the like; monoglycerides, such as glyceryl myristate, glyceryl palmitate lactate, and the like; polyglyceryl esters, such as polyglyceryl-6-distearate, polyglyceryl-4-oleyl ether, and the like, polyhydric alcohol ester ethers, such as methyl glucet-20 sesquiestearate, sucrose distearate; and analogues; sorbitan / sorbitol esters such as polysorbate-20, polysorbate-60, sorbitan sequiysostearate, and the like; and phosphoric acid triesters, such as tridecet-3 phosphate, triolet-8 phosphate, and the like. Exemplary ethers include ethoxylated alcohols, such as Cetearet-10, Cetet-10, Cetet-20, Isocetet-20, Estearet-10, Estearet-16, Estearet-20, Estearet-25, Olet-2, Olet-10, Olet- 20, nonoxynol-9, and the like; ethoxylated lanolin, such as PEG-20 lanolin, PPG-12-PEG-65 lanolin oil, and the like; ethoxylated polysiloxanes, such as dimethicone copoliol, and the like; propoxylated POE ethers, such as meroxapol 314, poloxamer 122, PPG-5-ketet-20, and the like; and alkyl polyglycosides such as lauryl glucose and the like.

Nonionic surfactants may be used as gelling agents, stabilizers, emulsifiers, suspending agents, solubilizers, foam enhancers, and in some cases as hydrotropic. Non-limiting examples of generally preferred nonionic surfactants include straight or branched alcohol ethoxylates, C8 to C11 alkylphenyl alkoxylates such as alkylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers, and the like; Cg to C22 fatty acid esters of polyoxyethylene glycol mono- and diglycerides; sorbitol esters and ethoxylated sorbitol esters; glycol esters of C8 to C22 fatty acid; ethylene oxide and propylene oxide block copolymers; and analogs. Nonlimiting examples of surfactant or hydrotropic enhancers include alkanolamides such as acetamide MEA, monoethanolamide, diethanolamide, lauramide DEA, cocamide MEA, cocamide DEA, isopropanolamide, and the like; amine oxides such as hydrogenated talolamine oxide; lower alkyl aryl sulfonates such as sodium toluene sulfonate; sulfosuccinates, such as disodium stearyl sulfosuccinate; and analogs.

The cationic polymer embodiments of the present invention are surprisingly compatible with cationic surfactants and other advantageous cationic compounds as antistatic agents. The term "antistatic agents" refers to ingredients that alter the electrical properties of cosmetic raw materials or surfaces of the human body (skin, hair, etc.) and textiles, for example by reducing their tendency to acquire an electric charge and thus can condition hair, skin, fiber and tissues. The cationic compatibility of the cationic polymer embodiment makes them advantageous for incorporation into formulations containing antistatic agents typically employed in hair care compositions such as shampoos, conditioner rinses after shampooing, leave-on products. application site] such as hair sprays, haircovers, and the like. The antistatic agent may be employed in amounts of up to about 30% by weight of the final composition, but is not limited thereto.

Antistatic agents include, but are not limited to, quaternary ammonium compounds, protein derivatives, synthetic quaternary ammonium polymers, amines, protonated amine oxides, betaines, silicones and silicone derivatives, and the like, which may act as anti-static agents. static in specific formulations and under controlled pH conditions in addition to any surfactant properties imparted by said materials. In addition to previously discussed antistatic agents, non-limiting examples of quaternary ammonium compounds useful as antistatic agents are acetamidopropyl trimmonium chloride, beenamidopropyl dimethylamine, beenamidopropyl ethyldimonium ethosulfate, beenotrimonium chloride, cetetyl morpholinium ethosulfate, cetrimonium chloride , cocoamidopropyl ethyldimmonium ethosulfate, diketethymmonium chloride, hydroxypropyl trimmonium dimethicone chloride, hydroxyethyl beenamidopropyl dimonium chloride, quaternium-26, quaternium-27, quaternium-63, quaternium-70, quaternium-72, collagen hydrate -76, PPG-9 diethylmonium chloride, PPG-25 diethylmonium chloride, PPG-40 diethylmonium chloride, stearalconium chloride, stearamidopropyl ethyl dimmonium ethosulfate, steardimonium hydroxypropyl hydrolyzed wheat protein, steardimmonium hydrolyzed collagen, wheat germamidopropalconium chloride, wheat germamidopropyl ethydymmonium ethosulfate, amodimethicone, and the like.

Quaternary ammonium synthetic polymers include film-forming polymers and conditioning polymers. Non-limiting examples of synthetic quaternary ammonium polymers include dimethyl dialyl ammonium chloride polymers and copolymers such as polyquatemium-4, polyquatemium-6, polyquatemium-7, polyquatemium-10, polyquatemium-11, polyquatemium-15, polyquatemium -16, poliquatemium-24, poliquatemium-28, poliquatemium-32, poliquatemium-33, poliquatemium-35, poliquatemium-37, poliquatemium-39, poliquatemium-44, poliquatemium-55, poliquatemium-60, poliquatemium- 65, poliquatemium-67 , polyquatemium-68, PEG-2-cocommonium chloride, quaternium-52, and the like. The term "hair fixing composition" or "hair shaping composition" comprises products comprising at least one polymer of the present invention as a hair fixing agent, which are applied to the hair (dry or wet) before, during or after the setting of the hair. hair to the desired shape (curly or straight), without limitation on the shape of the product.

The polymers of the present invention are surprisingly useful in hair-setting and hair-styling compositions as the sole conditioning agent, film-forming agent, rheology modifier, fixing conditioner, or may be used in combination with a hair-modifying auxiliary agent. rheology. The polymers of the present invention are also useful in combination with commercially obtainable hair-fixing auxiliary polymers, such as nonionic, anionic, cationic, and amphoteric hair-fixing polymers, cationic, structuring conditioning polymers, and combinations thereof to enhance the characteristics of hair fixation and hair styling. Conventional hair-fixing polymers and hair styling polymers, well known in the art, include natural gums and synthetic or anionic neutral resins and polymers.

Listings of commercially obtainable hair-setting polymers and hair-setting conditioning polymers can be found easily in the INCI Dictionary, Cosmetic, Toiletry and Fragrance Association (CTFA) listings, supplier websites, and trade literature. . See, for example, Polymer Encyclopedia published in Cosmetics & Toiletries®, 117 (12), December 2002 (Allured Publishing Corporation, Carol Stream, IL), the relevant disclosures of which are incorporated herein by reference.

Advantageous and commercially obtainable (ie, neutral) nonionic polymers used as hair styling or fixing polymers include, without limitation, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone / vinyl acetate copolymer (PVP / VA), VP / methacrylamide / vinyl imidazole (Luviset® Clear, BASF), carbohydrates (eg monosaccharides, disaccharides, and polysaccharides), and the like.

Advantageous anionic fixing polymers (ie, supplied in pre-neutralized form or formed in situ by base neutralization) are disclosed in US Patent 6,410,005, and International Patent Application No. WO 03/061615 which are incorporated herein by reference. .

Said fixing polymers are commercially available from Noveon, Inc., Cleveland, OH, and are sold under the trademarks Fixate® G-100 (supplied in neutralized form), INCI Nomenclature: AMP-acrylates / allyl methacrylate copolymer and Fixate® PLUS (supplied as a low pH emulsion), INCI Nomenclature: polyacrylate-14. Other examples of anionic fixing polymers are acrylate copolymers (Luviflex Soft and Luvimer from BASF; Avalure® AC series from Noveon, Inc.), and PEG / PPG-25/25 dimethicone / acrylates copolymer (Luviflex® Silk, BASF) and acrylamide / sodium acryl dimethyltaurate / acrylic acid copolymer (Acudyne®SCP, Rohm and Haas), sodium acrylamidomethyl methacrylic acid / propane sulfonate copolymer (Fixomer®, Nalco), and dehydroxanthan gum (Amaze ™, National Starch).

Commercially obtainable cationic fixing polymers include, but are not limited to, polymers bearing the INCI name, polyquatemium, such as polyquatemium-4, a diallyldimonium chloride / hydroxyethylcellulose copolymer (such as CELQUAT® H-100, National Starch); polyquatemium-11, a chimerized vinyl pyrrolidone / dimethylaminoethyl methacrylate chromized copolymer (such as GAFQUAT® 734, 755, 755N, ISP); polyquatemium-16, a quaternized vinyl pyrrolidone / vinylimidazole chloride quaternized copolymer (such as LUVIQUAT® FC-370, BASF); polyquatemium-28, a vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer (such as GAFQUAT® HS-100, ISP); polyquatemium-46, a chimerized vinylcaprolactam chimerized copolymer / vinylpyrrolidone / methylvinylimidazolium methosulfate; polyquatemium-55, a quaternized vinylpyrrolidone / dimethylaminopropylmethylacrylamide / lauryl dimethyl propyl methacrylamidoammonium chloride quaternized copolymer (such as STYLEZE ™ W-20, ISP); 1-vinylimidazole (as Luviquat® Supreme, BASF), and the like; and amino-substituted polymers that are cationic under acidic pH conditions, such as vinylcaprolactam / PYP / dimethylaminoethyl methacrylate copolymer (such as GAFFIX® VC-713, ISP); VP / dimethylaminoethyl methacrylate copolymer (as copolymer 845, ISP), PVP / DMAPA acrylate copolymer (as STYLEZE ™ CC-10, ISP), the chitosan pyrrolidone carboxylic acid salt, having the INCI name, Chitosan PCA (as KYTAMER®) PC, Amerchol), and the like.

Advantageous amphoteric fixing polymers include, but are not limited to, octyl acrylamide / acrylates / butylaminoethyl methacrylate copolymer (such as ANFOMER®, National Starch polymers), acrylate / lauryl acrylate / stearyl acrylate / methacrylate copolymers (ethyl ether oxide polymers) Clariant Corp., and Yokoformer ™ of Mitsubishi Chemical Corporation), and the like.

Advantageous commercial conditioning polymers include polymeric quaternary ammonium salts such as, but not limited to, polyquatemium-7, a polymeric quaternary ammonium monomer salt of monomers and dimethyl diallylammonium chloride monomers (such as MACKERNIUM ™ -007, Mclntyre Group, Ltd. ); polyquatemium-10, a hydroxyethylcellulose polymeric quaternary ammonium salt reacted with a trimethylammonium substituted epoxide (such as the JR, LK, LR, SR, Amerchol and CELQUAT® SC series, National Starch series UCARE® polymers); polyquatemium-39, a polymeric quaternary ammonium salt of acrylic acid, diallyl dimethylammonium chloride and acrylamide (such as MERQUAT® and MERQUAT® Plus polymers, Ondeo Nalco); quaternized derivatives of natural gums, e.g. guar hydroxypropyltrimonium chloride (such as JAGUAR® and JAGUAR® Excel polymers, Rhodia, Inc.), and the like.

The personal care compositions of the present invention, particularly the hair and skin care embodiments, may optionally contain guerbet esters as a gloss and radiance enhancer. Guerbet esters also provide emollient properties and impart desirable sensory properties such as soft feel and soft, sleek and healthy appearance. Guerbet esters are obtained from the reaction product of a Guerbet alcohol and a fatty acid. Exemplary Guerbet esters include octyldodecyl beeswax, octyldodecyl isostearate, octyldodecyl ricinoleate and trioctyldodecyl citrate. Guerbet esters are commercially obtainable from Noveon, Inc. sold under the trademarks Beesbutter® and Ultracas® G-20 and G-66.

Quaternary ammonium compounds are used for tissue conditioning and tissue care, commonly referred to as tissue softening agents, and are typically employed in amounts of up to about 20% by weight of the total formulation weight, but without limitation. themselves to them. Tissue softening agents useful in combination with the cationic polymers of the present invention generally include long chain alkylated quaternary ammonium compounds such as quaternary dialkyl dimethyl ammonium compounds, quaternary imidazoline compounds, quaternary amidoamine compounds, dialkylated derivative dihydroxypropyl compounds ammonium; quaternized dialkylester derivatives of ammonium methyltriethanol compounds, amine amide ester compounds, and quaternary dimethyl dimethylethanol chloride diester quaternary derivatives, as described in the Whalley review article, "Tissue Conditioning Agents", HAPPI, pp. 9-13. 55-58 (February 1995), incorporated herein by reference.

In addition to the antistatic agents previously discussed, non-limiting examples of quaternary dialkyl dimethyl ammonium compounds include N, N-dioleyl-N, N-dimethylammonium chloride, N, N-ditalolyl-N, N-dimethylammonium chloride, N, N-di (hydrogenated talolyl) -?,? -Dimethylammonium, and the like. Nonlimiting examples of quaternary imidazoline compounds include 1N-methyl-3-N-talolamidoethylimidazolium chloride, 3-methyl-1-talolylamidoethyl-2-talolylimidazolium methyl sulfate obtainable from Witco Chemical Company under the tradename VARISOFT® 475, and analogues. Non-limiting examples of quaternary amidoamine compounds include N-alkyl-N-methyl-N, N-bis (2-talolamidoethyl) ammonium salts wherein the alkyl group may be methyl, ethyl, hydroxyethyl, and the like. Non-limiting examples of quaternary dialkyl ester derivatives of dihydroxypropyl ammonium compounds include 1,2-ditaloloyloxy-3-N, N, N-trimethylamoniopropane chloride, 1,2-dichloyloyloxy-3-N, N, N-trimethylamoniopropane chloride , and the like.

Additionally, other types of long chain alkylated quaternary ammonium compounds (e.g., natural oil and fatty acid derivatives) are advantageous tissue softening agents, including, but not limited to, N, N-di (alkyloxyethyl) salts. ) -N, N-dimethylammonium, such as N, N-di (talolyloxyethyl) -N, N-dimethylammonium chloride, N, N-di (canolyloxyethyl) -N, N-dimethylammonium chloride, and the like; N, N-di (alkyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium salts such as N, N-di (talolyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium chloride N, N-di (canolyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium, and the like; N, N-di (2-alkyloxy-2-oxoethyl) -N, N-dimethylammonium salts such as N, N-di (2-talolyloxy-2-oxoethyl) -N, N-dimethylammonium chloride N-di (2-canolyloxy-2-oxoethyl) -N, N-dimethylammonium, and the like; N, N-di (2-alkyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium salts, such as N, N-di (2-talolyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium chloride, N, N-di (2-canolyloxyethylcarbonyloxy) chloride ) -N, N-dimethylammonium, and the like; N- (2-alkanoyloxy-2-ethyl) -N- (2-alkyloxy-2-oxoethyl) -N, N-dimethyl ammonium salts, such as N- (2-talolooyloxy-2-ethyl) -N- (2-talolyloxy-2-oxoethyl) -N, N-dimethyl ammonium, N- (2-canoloyloxy-2-ethyl) -N- (2-canolyloxy-2-oxoethyl) -N, N-dimethyl ammonium chloride, and analogues; N, N, N-tri (alkyloxyethyl) -N-methyl ammonium salts such as N, N, N-tri (talolyloxyethyl) -N-methylammonium chloride, Ν, Ν, Ν-tri (canolyloxyethyl) -N chloride methylammonium, and the like; N- (2-alkyloxy-2-oxoethyl) -N-alkyl-N, N-dimethyl ammonium salts, such as N- (2-taloyloxy-2-oxoethyl) -N-talolyl-N, N-dimethyl ammonium chloride (2-Canolyloxy-2-oxoethyl) -N-canolyl-N, N-dimethyl ammonium N-chloride, and the like.

Preferably long chain alkyl groups are derived from talol, canola oil, or palm oil, however, other alkyl groups derived from soybean oil and coconut oil, for example, are also advantageous, such as lauryl, oleyl, ricinoleyl, stearyl, palmityl, and similar fatty alkyl groups. Quaternary ammonium salt compounds may have any anionic group as a counterion, for example chloride, bromide, methosulfate (i.e. methylsulfate), acetate, formate, sulfate, nitrate, and the like.

Examples of preferred quaternary ammonium tissue softener compounds include N-methyl-N, N-bis (talolamidoethyl) -N- (2-hydroxyethyl) ammonium methyl sulfate and N-methyl-N, N-bis (hydrogenated talolamidoethyl) methyl sulfate -N- (2-hydroxyethyl) ammonium, each of these materials being available from Witco Chemical Company under the tradename VARISOFT® 222 and VARISOFT® 110, respectively; dialkyl esterquat derivatives of ammonium methyltriethanol salts, such as the DEHYQUART® AU series of Cognis bis (acyloxyethyl) hydroxyethyl methylammonium methosulfate ester quaternates such as DEE1YQUART® AU35, AU46, AU56, and the like; and N, N-di (taloloyloxyethyl) -N, N-dimethylammonium chloride, wherein the talol chains are at least partially unsaturated. Other preferred tissue softening agents include the well-known dialkylmethyl ammonium salts such as N, N-ditalolyl-N, N-dimethyl ammonium methyl sulfate, N, N-di (hydrogenated talolyl) -N, N-dimethyl ammonium chloride, N, N-distearyl-N, N-dimethyl ammonium chloride, N, N-dibeenyl-N, N-dimethylammonium chloride, N, N-di (hydrogenated talol) -N, N-dimethyl ammonium chloride (trade name ADOGEN® 442), N, N-ditalolyl-N, N-dimethyl ammonium chloride (trade name ADOGEN® 470, PRAEPAGEN® 3445), N, N-distearyl-N, N-dimethyl ammonium chloride (trade name AROSURF® TA-100), all obtainable from Witco Chemical Company; N, N-dibeenyl-N, N-dimethyl ammonium chloride, sold under the tradename Q Q-2802C by the Humko Chemical Division of Witco Chemical Corporation; and N, N-dimethyl-N-stearyl-N-benzylammonium chloride marketed under the tradename VARISOFT® SDC by Witco Chemical Company and AMMONYX® 490 by Onyx Chemical Company.

Any of the foregoing fabric softening agents, and mixtures thereof, may be used in combination with the polymers of the present invention, particularly in laundry and fabric care products. For ester containing fabric softening agents, the pH of the compositions may influence the stability of the fabric softening agents, particularly under prolonged storage conditions. The pH as defined in the present context is measured under pure conditions at about 20 ° C. In one embodiment, the pH of the composition is below about 6. In another embodiment, the pH is in the range from about 2 to about 5, and in another embodiment from about 2.5 to about 3, 5

In addition to previously described protein derivatives, non-limiting examples of protein derivatives include hydroxypropyl cocodimon hydrolyzed casein, hydroxypropyl cocodimon hydrolyzed collagen, hydroxypropyl cocodimon hydrolyzed hair keratin, hydroxypropyl cocodimon hydrolyzed rice protein , hydroxypropyl cocodimon hydrolyzed soy protein, hydroxypropyl cocodimon hydrolyzed wheat protein, hydroxypropyl cocodimon hydrolyzed silk amino acids, hydroxypropyl trimonium hydrolyzed collagen, hydroxypropyl trimonium hydrolyzed keratin, hydroxypropyl trimonium hydrolyzed rice bran , hydroxypropyl trimonium hydrolyzed soy protein, hydroxypropyl trimonium hydrolyzed vegetable protein, hydroxypropyl trimonium hydrolyzed wheat protein, soy ethyldimonium ethosulfate, soybean-ethyl morpholinium ethosulfate, and the like. It is possible to add a pH adjusting agent to either a previously swollen, base swollen, or water swollen polymer or to a formulation containing a polymer embodiment of the invention. Thus, the pH adjusting agent may be used in any amount necessary to obtain a desired pH value in the final composition. Non-limiting examples of alkaline pH adjusting agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Ammonium hydroxide; organic bases such as triethanolamine, diisopropylamine, dodecylamine, diisopropanolamine, aminomethyl propanol, cocamine, oleamine, morpholine, triamylamine, triethylamine, tromethamine (2-amino-2-hydroxymethyl) -1,3-propanediol), and tetraquiis (hydroxypropyl) ethylen; and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like, and mixtures thereof. Acid pH adjusting agents may be organic acids, including amino acids, and inorganic mineral acids.

Non-limiting examples of acidic pH adjusting agents include acetic acid, citric acid, fumaric acid, glutamic acid, glycolic acid, hydrochloric acid, lactic acid, nitric acid, phosphoric acid, sodium bisulfate, sulfuric acid, tartaric acid, and the like. , and mixtures thereof.

The polymers of the present invention may be used as a thickener, film former, or as a dye or pigment suspending agent to promote dye deposition on hair and skin. Hair dyes can be temporary, semi-permanent or permanent hair dyes or color restorers that gradually pigment the hair. Temporary and semi-permanent hair dyes are typically rinses, gels, sprays, shampoos, sticks, and the like, and hair color restorers are typically in the form of hair emulsions or coatings. Permanent hair dyes, and more durable semi-permanent hair dyes, are generally two-part products, one part containing oxidative dye intermediates and dye couplers, and the other part containing stabilized oxidizing agent, usually hydrogen peroxide. at about pH 3-4, and are mixed together immediately prior to use. It is well known that said two-part hair dye products are formulated with combinations of surfactant ingredients, usually nonionic surfactants or anionic surfactants, to thicken when the dye mixture is prepared. In addition to the preceding literature, a general discussion of hair dyeing chemistry and compositions is found in Brown et al, SCC monograph, "Permanent Hair Dyes", Society of Cosmetic Chemists (1996), incorporated herein by reference. The polymers of the present invention may be incorporated into one or both of the two parts of said hair dyeing systems, either as the thickener for the acid stabilized oxidizing portion or in the non-oxidizing portion to be thickened upon mixing with the hair dye. acidic portion.

In addition to ingredients discussed above, other ingredients commonly used for anti-acne products, facial and body hair whiteners, and antiseptic products include oxidizing agents such as hydrogen peroxide, benzoyl peroxide, and water-soluble inorganic persulphate compounds such as persulphate. of ammonium, potassium persulphate, and sodium persulphate.

The polymers of the present invention are useful silicone fluid stabilizers which are commonly used in shampoo products, such as the so-called "two-in-one" combination of shampoo / conditioner shampoos. Silicone fluids are generally described as alkylsiloxane polymers. The most common class of silicone polymers are linear polydimethyl siloxanes having the general formula CH3- (Si (CH3) 2-0) w-Si (CH3) 3 where w indicates an integer greater than 2. Silicones may also be branched materials wherein one or more alkyl groups in a polymer are replaced by oxygen to create a branch point. Silicone fluids are typically water-insoluble oils having a viscosity in the range of a few mPa s to several thousand mPa s.

A particularly useful class of silicones for use in hair care products are so-called rigid silicones (also known as silicone gums), as described, for example, in US Patent 4,902,499, incorporated herein by reference, which generally contain A viscosity (at about 20 ° C) above about 600,000 mPa has an average weight average molecular weight of at least about 500,000 Daltons as determined by intrinsic viscosity measurement. The polymers of the present invention are surprisingly effective for stabilizing two-in-one shampoo formulations containing rigid silicone conditioning agents.

Another class of silicone materials that are particularly useful in combination with the polymers of the present invention comprises volatile silicones, which are often used as lubricants in hair care products such as shampoos. Volatile silicones include cyclic and linear polydimethylsiloxanes, and the like. Volatile cyclic silicones typically contain about 3 to about 7 silicon atoms, alternating with oxygen atoms, in a cyclic ring structure. Each silicon atom is also replaced by two alkyl groups, typically methyl groups. Linear volatile silicones are silicone fluids, as described above, having viscosities no greater than about 25 mPa s. A description of volatile silicones is found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics, Cosmetics and Toiletries", vol. 91, pp. 29-32, 1976, and in Kasprzak, "Volatile silicones", Soap / Cosmetics / Chemical Specialties, p. 40-43, December 1986, each incorporated herein by reference.

Other silicone oils include dimethicone copolyols, which are linear or branched dimethylsiloxane copolymers (dimethicone) and alkylene oxides and may be functionalized via a hydroxyl group on a terminal alkylene oxide unit.

Dimethicone polyols may be random or block copolymers. A generally useful class of dimethicone polyols comprises block copolymers having polydimethylsiloxane blocks and polyalkylene oxide blocks, such as polyethylene oxide blocks, polypropylene oxide, or both. Silicone fluids, including volatile silicones, silicone gums, and silicone copolymers, are obtainable from a variety of commercial sources, such as Dow Corning, General Electric Company, and Noveon, Inc.

Other oily materials which are useful in combination with the polymers of the present invention include, for example, acetylated lanolin alcohols; lanolin alcohol concentrates; lanolin fatty acid esters, such as lanolin fatty acid isopropyl esters; polyol fatty acids; ethoxylated alcohols, such as ethoxylate and castor oils; sterols; sterol esters; sterol ethoxylates; and analogous materials. Many of these esters and ethoxylates are also useful as nonionic surfactants.

Numerous ingredients are known in the art as hair or skin conditioning agents, and wetting agents, and, in addition to those previously discussed, non-limiting examples include PCA (DL-pyrrolidone carboxylic acid) and its salts such as lysine PCA, aluminum PCA, copper PCA. chitosan PCA, and analogs, allantoin; urea; hyaluronic acid and its salts; ceramides; sorbic acid and its salts; sugars and starches and derivatives thereof; lactamide MEA; and analogs.

Although overlapping weight ranges for the various components and ingredients that may be contained in the compositions of the invention have been expressed for selected embodiments and aspects of the invention, it should be readily understood that the specific amount of each component in the surfactant-containing composition will be selected from. its range is described such that the amount of each component is adjusted such that the sum of all components in the composition will total 100% by weight. The amounts employed will vary according to the purpose and character of the desired product and can be readily determined by one of skill in the formulation arts and literature.

It is also recognized that the choice and amount of ingredients in personal care, home care and industrial care compositions including the polymers of the invention may vary depending upon the desired product and its function, as is well known to those skilled in the art. of the formulation. An extensive listing of ingredients and their conventional functions and product categories has already been disclosed, and can be easily determined in the literature.

The following examples are presented for purposes of illustrating the invention disclosed in more detail herein. However, the examples should not be construed as limiting the invention in any way.

Unless otherwise specified, all parts are by weight, and the term "level" means% by weight.

Method Description Transparency When reported, the transparency of the polymer containing composition was measured in% T (transmittance) with a Brinkmann PC 920 calorimeter at least about 24 hours after preparation of the composition.

Transparency measurements against deionized water (100% transparency) were collected. Compositions having a transparency of about 60% or more were substantially transparent; Compositions having a transparency in the range of about 45 to 59% were judged to be substantially translucent.

High Humidity Curl Retention (HHCR) retention test The strength of a polymer fixative composition under high humidity (about 90% relative humidity (RH)) is measured according to with its ability to attach a curl made to the hair even after absorption of water from the applied composition and the surrounding atmosphere, employing the well known technique which is commonly referred to as high moisture curl retention (HHCR). Descriptions of HHCR methodology are readily found in the cosmetic literature (see, for example, chapter 30, Harry's Cosmeticology, 8th ed., MJ Rieger, Ph.D. (ed.), Pp. 666-667, Chemical Publishing Co. , Inc., New York, NY, 2000, and Diaz et al., J. Soc.

Cosmet. Chem., 34, pp. 205-212, July 1983, the relevant disclosures of which are incorporated herein by reference.

Commercially mixed untreated (virgin) human hair bundles are prepared using natural black and brown Oriental and / or European hair supplied by International Hair Importers and Products Inc., New York. Each bundle of hair (about 2.5 grams in weight) is about 7.5 inches (19.5 cm) long and is attached (at the root portion height) to a metal clip equipped with a strap. wire gain. Prior to use, each beam is washed with a dilute aqueous sodium lauryl sulfate solution (10% SLS) followed by careful rinsing with room temperature deionized water. The bundles are dried by towel absorption. The initial extended length of the hair bundle (Le) is measured and recorded.

Variable amounts of the polymeric fixing composition to be evaluated are applied to each hair bundle. The polymeric fixative composition to be evaluated is applied to the hair bundle and distributed evenly from the root portion of the hair to the tip portion. The treated hair bundle is wrapped around a hair curler having an outside diameter of about 3 cm and dried for 12 hours at room temperature of about 21 to 23 ° C. After drying, the curler is carefully removed, leaving the hair bundle shaped into a single curl, the initial length of the curl (Lj) being measured and recorded. The curly hair bundle is hung vertically in a humidity chamber set at a temperature of about 26 ° C and a relative humidity level of 90%. Curl retention in high humidity conditions is determined by measuring the length of the curl as the curl relaxes. Measurements are taken at selected time intervals (Lt) over a continuous 24 hour exposure to high humidity. The following equation is used to calculate the percent retention of curls relative to the initial curl length (Lj) and the length of the fully extended hair before curling (Le):% curl retention = Le -Lt / Le - Lj x 100 The change in bunch length (collapse, helix formation) is measured periodically at selected intervals and is monitored over a 24 hour period. At time zero an initial measurement was taken, followed by measurements at 0.25 hour intervals for the first hour of exposure, followed by measurements after 0.5 hour intervals at the second hour of exposure, followed by measurements taken at 1.0 hour intervals during the remaining 22 hours of exposure.

Curly retention of about 70% or more for a minimum of about 0.75 hours at about 90% RH [relative humidity] is a conventional feature for good resistance to high humidity conditions, and superior HHCR 70% after a period of at least about 3 hours is considered very good to excellent.

High Humidity Spiral Curl Retention Test (HHSCR) Retention Test Although the moisture resistance of a fixative composition can be assessed with the HHCR test described above. The HHCR test is performed using regular salon-type curlers, where the hair curls on itself as it is curled, which protects the fibers inside the curl from the test environment. Curly retention testing can be made more stringent through the use of spiral curlers. With this modification, the hair is wound into a spiral groove along the longitudinal axis of the curling shaft without overlapping.

Thus, in the case of a spiral curl, the entire length of the hair is fully exposed to the environment.

The same materials, methods, and assessment techniques outlined for the previously described HHCR test are used for the HHSCR test, except that the hair bundle weighs 0.5 g, is 6.5 inches (16.51 cm ) is longer and is wound around a spiral perm rod (Cyber Sprials ™ large spiral curling rods, 8 mm inner diameter, 13.5 mm outer diameter, 162 mm long, American Discount Beauty Supply, 269 South Beverly Drive # 250, Beverly Hills, CA). Results are reported as percent curl retention calculated using the curly retention equation presented above.

Curly retention of about 70% or more for a minimum of about 0.75 hours at about 90% relative humidity is a conventional feature for good strength in high humidity conditions, and an HHCR of over 70%. After a period of at least about 3 hours it is considered very good to excellent.

High Humidity Stiffness Retention Test (HHSR) The Stiffness Retention Test is performed by attaching a fixative-treated hair sample (test sample) to a support structure (Figure 5 ) that keeps the test sample flexed at an angle of 45 °. The test sample is placed in a humidity chamber set at a temperature of about 26 ° C and a relative humidity level of 90%. Retention of stiffness in high humidity conditions is determined by measuring the collapse in the test sample as the hair sample relaxes when exposed to wet conditions. Measurements are taken at selected time intervals (Ht) over a continuous 24 hour exposure to high humidity conditions. The following equation is used to calculate the stiffness retention percentage relative to the initial sample height (¾) and the sample height obtained at each time interval (Ht)% stiffness retention = H; -Ht / H; x 100 The change in sample height is measured periodically at selected intervals and is monitored over a 24 hour period. Sample height is the distance from the bottom of the mounting platform to the tip of the test sample. An initial measurement is taken at time zero (before exposure to moisture), followed by measurements at 0.25 hour intervals for the first hour of exposure, followed by measurements taken at 0.5 hour intervals for the second hour of exposure. exposure, followed by measurements taken at 1.0 hour intervals during the remaining 22 hours of exposure.

A stiffness retention value of about 70% or more over a minimum period of about 0.75 hours at about 90% relative humidity is a conventional feature for good strength at high humidity concentration, and superior retention value. 70% after a period of at least about 3 hours is considered very good to excellent.

Test hair samples (6.5 inch length, 16.51 cm), weight 2.5 g) consisting of virgin Asian or European hair are attached with a flat fixation (sewn and waxed) such that sample has a uniform rectangular cross-section over its entire length (a ribbon-like configuration). The samples are washed with a removal shampoo containing 10% by weight of ammonium lauryl sulfate and rinsed with deionized water. A determined amount of experimental fixative is homogeneously applied to wet hair samples. The samples are plant-laid on Teflon® sheet to dry at 23 ° C and 50% relative humidity for 16 hours.

Dummy Head Hair Modeling Selection To determine the modeling effectiveness of the inventive polymer fixation gel embodiments with respect to the hard fixation, stiffness, and curl retention properties under high humidity conditions, the following test was performed. Selection: Human hair implanted in plastic mannequin heads is modeled and evaluated according to the procedure below: 1) The hair of each mannequin head is washed with shampoo (Quantum Clarifying Shampoo), Zotos International, Inc .) and is rinsed 3 times with deionized water. 2) Damp hair is parted in the middle (front to back) of the dummy head, and equal portions of hair are combed to each side from the midline. Along each side of the parting line is a grid consisting of 1 x 1 inch (2.54 cm) squares arranged in two rows of 3 squares each. Row 1 is parallel and contiguous to the midline, and row 2 is parallel and contiguous to row 1. 3) From the left side of the central part (looking towards the face of the dummy's head) 3 hair ends are formed inside row 1 of the grid while the hair is still wet. The ends are formed by joining the hair into a section of the grid measuring 1 x 1 inch (2.54 cm), bundling it into a beam, working a desired amount of the experimental modeling composition into a beam until the composition is dispersed. homogeneously over the hair, and combing the hair bundle upward from the scalp of the dummy head to the tip of the bundle to form one end. The process is repeated for the other grid sections in the row, with the same amount of experimental modeling composition worked on each beam.

In row 2 of the grid, bundles are formed while the hair is still damp and treated in each section of grid as described above. Each bundle is wound into a curl (PLASTIC SNAP-ON ROLLERS), 5/8 inch (1.58 cm) diameter x 2 V4 inch (5.71 cm) long ). 4) Step (3) is repeated on the right side of the head of the dummy except that a commercially obtainable polymeric fixative is applied to the respective hair bundles for comparison purposes. 5) A rubber alloy is placed around the untreated hair to hold it in place and the head of the mannequin is inverted upside down and suspended in a holder allowing the hair ends to hang freely. The hair is allowed to air dry for 12 hours at room temperature at 50% relative humidity. 6) After drying the rollers are removed from the dummy's hair. 7) The modeled mannequin heads are placed in a humidity chamber set at 35 ° C and 90% relative humidity. 8) Mannequin heads are evaluated at 1, 2 and 3 hour intervals to determine curl stiffness and retention. Mechanical Stiffness Test Method A TA XTPlus Texture Analyzer (Stable Micro Systems, Surrey, UK) texture analyzer equipped with a rectangular loading nose (3 mm thick x 70 mm wide x 99 mm high) and a 3-point flexing is employed to evaluate the mechanical stiffness of a fixer-treated hair bundle. The texture analyzer is interfaced with a personal computer loaded with Texture Exponent 32 data acquisition software that collects and analyzes the data entered by the instrument. The flexing structure consists of two parallel support legs which are approximately 25.4 mm apart. The treated hair sample test sample is centered between the support legs, and the loading nose that is centered above and between the support legs is pressed through the sample at a rate of 40 mm / s over a distance of 20 mm. mm Data acquisition begins when the loading nose contacts the sample. The data acquisition software calculates and records the amount of force (Newtons) required to flex the sample at a distance of 20 mm. Results are reported as Peak Force (N).

Hair samples (6.5 inches (16.51 cm) long, weight 2.5 g) consisting of virgin natural human hair are bonded with a flat (sewn and waxed) alloy such that the beam has a section uniform rectangular cross-section along its entire length. The bundles are washed with a removal shampoo containing 10% by weight of ammonium lauryl sulfate and rinsed with deionized water. A determined amount of experimental fixative is homogeneously applied to damp hair samples. A first set of samples is placed flat on a Teflon® sheet to dry at 23 ° C and 50% relative humidity in a controlled laboratory environment for 16 hours and tested. A second set of samples is similarly prepared and placed in a humidity chamber (Spec LHU-113) set at 23 ° C and 90% relative humidity for 16 hours and subsequently tested for mechanical rigidity.

Subjective rating is given for the specific Peak Force ranges (N) to classify the fixative polymer stiffness as follows: Glaze Transition Temperature (Tg) The glaze transition temperature (Tg) of the inventive polymers is determined by the well-known Differential Scanning Calorimetry (DSC) technique.

Turbidity When reported, the Turbidity of a polymer-containing composition was determined in Nephelometric Turbidity Units (NTU) using a distilled water nephelometric turbidity meter (NTU = 0) as the standard. Compositions having an NTU value of about 90 or greater were judged cloudy.

Viscosity The reported viscosity of each polymer-containing composition was measured in millipascals per second (mPa-s) using a Brookfield rotary screw viscometer (Brookfield, RVT) at about 20 revolutions per minute (rpm) at room temperature. enclosure at about 20 to 25 ° C (hereinafter referred to as Brookfield viscosity). Viscosity was measured in freshly prepared compositions (referred to as "initial viscosity", and again measured after allowing the composition to age for at least about 24 hours at room ambient temperature (referred to as "24-hour viscosity"). only one viscosity value, the viscosity value and the 24-hour viscosity unless otherwise indicated.

Yield value Yield value, also referred to as Yield S beam, is defined herein as the initial flow resistance under beam. It can be measured using a variety of techniques, such as using a constant beam rheometer or extrapolation using a Brookfield viscometer. These techniques and the utility of yield value measurement are further explained in the Noveon, Inc. Technical Data Sheet No. 244, incorporated herein by reference.

Material Abbreviations and Trade Names AA Acrylic Acid AAE5P5 A 5 / Ethoxylated Randomly Propylated Allyl Ether (BX-AA-E5P5, Bimax, Inc.) Acudyne® SCP Acrylamid / Acrylamidomethyl Propanesulfonic Acid (Sodium Salt) / Acid Copolymer methacrylic acid (Rohm and Haas) AMP-95 aminomethyl propanol (Angus) AMPS® 2-acrylamido-2-methylpropane sulfonic acid monomer APE alylpentaerythritol Arianor® Madder Red basic red dye 76, Cl n ° 12245 (Sensient Technologies Corporation) Arianor® SiennaBrown dye basic brown 17, Cl # 12251 (Sensient Technologies Corporation) Arianor® Steel Blue basic blue dye 99, Cl # 56059 (Sensient Technologies Corporation) Arlasolve ™ 200 surfactant isocetet-20 (Uniquema) Bam t-butylacrylamide BEM25 beenet-25 methacrylate Bio-Terge® AS-40 Sodium olefin sulfonate with from C1 to C16, 40% surfactant (Stepan Company) Bruggolite® FF6 hydroxymethane sulfate sodium dihydrate-reducing agent (Braggeman Chemical US) Carbopol® Ultrez 21 C10 to C30 Acrylate / Alkyl Acrylate Cross-Polymer Rheology Modifier (Noveon, Inc.) Carbopol® 940 Cross-linked Acrylic Acid Homopolymer Carbomer (Noveon, Inc.) Carbopol® 980 Cross-Linked Acrylic Acid Homopolymer Carbomer (Noveon, Inc.) Carbopol® 996 crosslinked acrylic acid homopolymer carbomer (Noveon, Inc.) Cetiol® 868 octyl stearate (Cognis Corp.) Chemonic ™ OE-2 olet-2 emulsifier (Noveon, Inc.) CitA citraconic anhydride CSEM25 cetearet-25 methacrylate DC 193 PEG-12 dimethicone copolyol (Dow Corning) DC 1401 Fluid cyclomethicone (e) dimethicone (Dow Corning) DC 1664 dimethicone emulsion (e) lauret-4 (e) lauret-23 (Dow Corning) DC 1784 dimethiconol emulsion (e) TEA-dodecylbenzenesulfonate (Dow Corning) DC5103 pending copolyol dimethicone (PEG-7 dimethicone), MW = 2,500, CAS No. 68937-54-2 (Dow Corning) DMAEMA N, N methacrylate '-dimethylaminoethyl Drakeol® 7 LT Light Mineral Oil (Penreco) E Emulgade® 1000 NI ethyl acrylate cetearyl alcohol (e) cetearet-20 EMULSOGEN® EPN 407 Cn secondary ethoxylate featuring 40 ethylene oxide units per alcohol unit (Clariant Corp.) FD&C Blue No. 1 Hilton Davis (Noveon) , Inc.) Finsolv® TN Cu C1 -C5 Alkyl Benzoate (Fintex Inc.) Fixate® Plus Polyacrylate-14 (Noveon, Inc.) Fixate®G100 AMP-Acrylates / Allyl Methacrylate Copolymer (Noveon, Inc.) Gafquat®755N polyquatemium-11 a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (International Specialty Products Corporation) GlydantPlus® mixture of 1,3-dimethylol-5,5-dimethyl hydantoin and iodopropinyl butyl carbamate (Lonza Group Ltd.) Germaben® II antimicrobial mixture glycol, diazolidinyl urea, methylparaben and propylparaben (International Specialty Products Corporation) Germaben® II-E an antimicrobial mixture of propylene glycol (e) diazolidinyl urea (e) methylparaben (e) propylparaben formulated for you emulsion grades (International Specialty Products Corporation) Herbasol® Aloe Vera Aloe Barbadensis Extract (Cosmetochem International Ltd.) Herbasol® Chamomile Recutite Chamomile Extract (Cosmetochem International Ltd.) Herbasol® Horsetail Equisetum Arvense Extract (Cosmetochem International Ltd.) Herbasol ® Stinging Nettle Urtica dioica extract (Cosmetochem International Nettle Ltd.) Herbasol® Tea Tree Melaleuca altemifolia extract (Cosmetochem International Ltd.) Herbasol® Witch Hazel Extract of Hamamelis virginian Cosmetochem International Ltd.) Hostapon® methyl oleyl sodium taurate (Clariant ) Hydramol ™ PGPL Polyethylene Glycol 400 Propoxylated Monolaurate Ester (Noveon, Inc.) IPA Isopropyl Alcohol ItA Itaconic Anhydride Kathon ™ CG Methyl Chloroisothiazolinone (e) Methylisothioazolinone Kollidon® K30 Polyvinylpyrrolidone Fixing Polymer (BASF)

Aktiengesellschaft) Gelatin Beaded Lipopearls ™ Vitamin E (Lipo Technologies Inc.) Luperox 11 M 75 t-Butyl peroxypivalate free radical initiator (75% solution in odorless minerals) (Atofina) Luviskol® K90 polyvinylpyrrolidone fixing polymer (BASF

Aktiengesellschaft) Luviskol® VA 73 vinylpyrrolidone / vinyl acetate copolymer Luviset® Clear N-vinylpyrrolidone, methacrylamide and N-vinyl imidazole copolymer (BASF Aktiengesellschaft) MAA methacrylic acid MalA maleic anhydride MMA Muratum methacrylate Mururu methacrylate oil of Astrocaryum murumuru (palm), (Chemyunion Qufmica Ltda) Neobee® M-5 tri caprylic / capric triglyceride (Stepan Company) Oam t-octylacrylamide Pantenol dl-pantenol 50 W (l-Methyl-4 (1,5- dimethyl-1-hydroxyhex-4 (5) -enyl) cyclohexene) 50% aqueous solution (BASF Aktiengesellschaft) Plantaren® 2000 decyl glucoside (Cognis Care Chemicals) Practice dummy head with 18-20 inch human hair ( 45.72 cm to 50.80 cm) long (manufactured by Marianna Industries; purchased from Sally Beauty Company, Inc.) Phenonip® antimicrobial mixture of methylparaben, ethylparaben, propylparaben, butylparaben and isobutylparaben, (Clariant-Nipa Laboratories) RAL 307 a randomly ethoxylated-30 / propoxylated-5 allyl ether Schercemol ™ DISF diisostearyl fumarate (Noveon, Inc.) SilSense ™ A-23 PEG-7 amodimethicone (Noveon, Inc.) SilSense ™ Copoliol -1 PEG-33 (e) PEG-8 Dimethicone (e) PEG-14 (Noveon, Inc.) SilSense ™ Q-Plus Quaternary-8 Silicone (dimethicone copolyol quaternized with an alkyl starch dimethylamine (Noveon, Inc.) Silsoft® 305 pending copolyol dimethicone (PEG-5 / PPG-3 methicone), MW - 600, CAS No. 134180-76-0, (GE

Silicones / OSi Specialties) Silsoft® 475 dimethicone copolyol pending (PEG-23 / PPG-6 dimethicone), MW = 19,000, CAS No 68937-55-3, (GE Silicones / OSi Specialties) Silsoft® 810 linear copolyol dimethicone (PEG -8 dimethicone), MW = 1,700, CAS No. 102783-01-7, (GE

Silicones / OSi Specialties) Silsoft® 895 dimethicone copolyol pending (PEG-17 dimethicone), MW = 5,000, CAS No 68937-54-2, (GE Silicones / OSi Specialties) Sipomer® WAMII methacrylamidoethyl-N-ethylene urea (Rhodia, Inc.) STY Styrene SucA Succinic Anhydride TEGDMA Triethylene Glycol Dimethacrylate Timiron® Splendid Gold Golden Mica Cosmetic Pigment, (EMD

Chemicals Inc. Gold RONA -Cosmetic Business Unit) Timiron® Diamond Cluster MP-149 bright gray-white mica / titanium dioxide powder (EMD Chemicals Inc. RONA - Cosmetic Business Unit) TMCHMA trimethyl cyclohexyl methacrylate (Ciba Specialty Chemicals) TMPEO15 TA trimethylolpropane PEG-15 triacrylate TMPTA trimethylolpropane triacrylate Ultracas® G-20 octyldodecyl ricinoleate ester guerbet, (Noveon, Inc.) Unispheres® YE-501 cosmetic beads containing tocopheryl acetate (e) lactose, cellulose (e) hydroxypropyl cellulose ) iron oxide (Induchem AG) Wecobee® hydrogenated vegetable oil (Stepan Company) Zinc Omadine® zinc pyrithione (Arch Chemicals, Inc.) Examples of SM 1 to SM 11 A. Synthesis of copolyol dimethicone macromer (without catalyst) Macromers Copolyol dimethicone (SM) containing terminal and pendant polyether groups according to Formulas III, Illa, IV, and IVa are synthesized by reaction of cyclic anhydrides and dimethicone copol Iols shown in Table IA.

A 2 1 glass reactor equipped with a mechanical stirrer, nitrogen inlet, temperature probe connected to an electronic controller, and a water condenser is charged with its copolyol dimethicone (Table IA). Under stirring the copolyol is heated to 80 to 105 ° C and extracted under vacuum for 15 minutes to 1 hour. The reactor is cooled to 80 to 85 ° C, evacuated with N2, and then the respective cyclic anhydride (Table IA) is loaded into the reactor. The stirred mixture is heated at 80 to 85 ° C for 1 to 3 hours. Then the mixture is extracted under vacuum for 15 minutes, evacuated with N 2, and cooled to 50 ° C.

Then the mixture is filtered to remove particulates. In each example, NMR spectroscopy analysis confirms the formation of the respective dimethicone copolyol carboxylate semiesters. B. Synthesis of Copoliol Dimethicone Macromer (with catalyst) Using an identical adjustment to the above catalyst-free synthesis procedure, dimethicone copoliol and anhydrous alkali metal acetate (0.7 g, 0.2% weight / weight of the total components of recipe) are heated at 80 ° C under vacuum for 15 minutes. After recharging with N 2, the mixture is allowed to react with the cyclic anhydride for 1 to 2 hours at 80 to 82 ° C.

NMR spectroscopic analysis confirms the formation of the respective copolyol dimethicone carboxylate semi-ester (Table 1B).

Examples 1 and 2 illustrate the volume homopolymerization of the two olefinically unsaturated (SM) copoliol dimethicone macromers of the invention. One macromer is derived from a substituted cyclic anhydride (i.e. itaconic anhydride) and the other macromer is derived from an unsubstituted cyclic anhydride (i.e. maleic anhydride).

Example I

A three-neck, round-bottomed flask, volume 100 ml with magnetic stirring, thermocouple is rinsed with nitrogen. The flask is charged with 30 g of the dimethicone copolyol macromer of Example SM 11 (Table 1B). An ammonium persulfate initiator solution (2.6 g in 25 g of water) is added in several portions at 4 hour intervals. The reaction was performed under continuous stirring at 80 to 85 ° C. It took 8 hours for approximately 50% of the macromer to convert to the homopolymer, and 16 hours for approximately 70% of the macromer to convert to the homopolymer. 1 H NMR analysis of CDCl3 extract of the polymer product indicates that unreacted itaconic anhydride derivatives are in the product.

Example II

Example I is repeated with the macromer of Example SM 7 (Table 1 B) except that 0.5% Luperox 11M 75 primer (based on total monomer weight) is added to the monomer mixture which is then heated to 60 ° C. . Within 10 minutes the reaction mass freezes after reaching an exotherm of 72 ° C. The DMC maleate derivative is much more reactive than the trisubstituted (methyl) maleate derivative of Example 1. 1 H NMR analysis of CDCI3 extract of this gel indicates that only a small portion of unreacted maleic anhydride remains in the product. reaction.

The following examples illustrate the copolymerization of the olefinically unsaturated (SM) copoliol dimethicone macromers of the invention with other olefinically unsaturated monomers such as AMPS, MMA, MAA and STY using solution and precipitation polymerization techniques.

Example III

A 500 ml volume jacketed reactor equipped with a condenser, thermocouple, mechanical stirring (half moon blade) and nitrogen blanket is loaded with 2 parts of the copolyol dimethicone macromer of Example SM 9, 28.5 parts of IPA, and 28.5 parts of distilled water.

Primer (0.2 parts Luperox 11M75 in 1 part IPA) is injected into the reactor at 72 ° C and a mixture of 18 parts AMPS 2405 monomer, 9 parts IPA, and 9 parts distilled water is dosed. over 3 hours. An initiator booster (0.02 parts Luperox 11M75 in 1 part IPA) is added hourly after the start of dosing. The addition of enhancer continued until the conversion of all reagents was confirmed by1 H-NMR. A clear product is obtained by neutralization with diluted AMP-95. The final product had a total solids content of 21.15% at pH 4.5.

Example IV

A jacketed 500 ml volume reactor equipped as in Example III is charged with 15 parts of the dimethicone copolyol macromer of Example SM 9a, 380 parts distilled water and 100 parts IP A.

Primer (0.4 parts Luperox 11M75 in 1 part IP A) is injected into the reactor at 80 ° C, and a mixture of 40 parts MMA and 20 parts MAA is dosed into the reactor via a pump. syringe.

A mixture of 25 parts of AMPS 2405 monomer and 25 parts of water is metered into the reactor via another syringe pump over the course of 3 hours. An initiator booster (0.06 parts Luperox 11M75 in 1 part IP A) is added hourly after initiation of dosing. The addition of enhancer continued until the conversion of all reagents was confirmed by NMR '. The final product has a total solids content of 21.94% at pH 8.9 and appears as translucent liquid after IP A extraction and neutralization with AMP-95.

Example V

A jacketed 500 ml volume reactor equipped as in Example IV is charged with 5 parts of the dimethicone copolyol macromer of Example SM 9, 190 parts distilled water and 190 parts IPA.

Primer (0.4 parts Luperox 11M75 in 1 part IPA) is injected into the reactor at 80 ° C, and a mixture of 55 parts styrene and 20 parts MAA is dosed into the reactor via a syringe pump. .

A mixture of 20 parts of AMPS 2405/10 parts of water is injected into the reactor by another syringe pump over the course of 3 hours.

An initiator booster (0.78 parts total of Luperox 11M75 in 1 part IPA) is added hourly after the start of dosing. A solid polymer is obtained and it is filtered and washed with 100 g IPA followed by 50 g IPA / water mixture and then dried. The final product is a white powder.

The following examples illustrate the copolymerization of the olefinically unsaturated (SM) copoliol dimethicone macromers of the invention with different types of monomers via anionic emulsion polymerization.

Examples VI to VIII

Emulsion polymers are prepared from the monomers shown in Table 2 as follows: A mixture of reaction monomers is prepared in a first reactor equipped with a stirrer spinning at about 900 rpm under a nitrogen atmosphere by combining 148 parts by weight of MAA, about 200 parts by weight of EA, and about 40.0 parts by weight of the macromer prepared in Example SM 7 to 192 parts by weight of deionized water containing about 13.3 parts by weight of 30. % aqueous sodium lauryl sulfate. In a second reactor equipped with a nitrogen inlet stirrer and feed pumps, about 580 parts by weight of deionized water and about 1.27 parts by weight of 30% aqueous sodium lauryl sulfate are added. The contents of the second reactor are heated with stirring at a rotation speed of about 200 rpm under a nitrogen atmosphere.

After the contents of the second reactor reach a temperature in the range of about 85 to 88 ° C, about 7.84 parts of 1.73% ammonium persulfate sulfate (free radical initiator) are injected into the heated surfactant solution. in the second reactor. The aqueous emulsion of the first reactor monomer mixture is gradually pumped into the second reactor over a period of about 180 minutes at a temperature in the range of about 85 to 88 ° C.

Simultaneously, a starter feed of about 60 parts by weight of 1.7% ammonium persulfate solution is dosed into the reaction mixture in the second reactor and the reaction temperature is maintained at about 90 ° C. for an additional hour and a half to complete the polymerization. The resulting emulsion is cooled to room temperature, discharged from the reactor and collected. All three copolymers are analyzed by NMR using CDCl3 extract. The copolymer of Comparative Example VII showed NMR peaks corresponding to nonreactive copolyol dimethicone succinate ester which is presumably not incorporated into the copolymer.

Surprisingly, the copolymers of Examples VI and VIII containing reactive double bonds did not show an unreacted maleate ester derivative (SM 7) or dimethylone ester unreacted itaconate derivative (SM 9) related functional ester peak. . These experiments illustrate that the macromers of the invention are readily copolymerizable to emulsion polymerization.

Examples of 1 to 3 Emulsion polymers are prepared as in Examples VI to VIII using the monomers and macromers shown in Table 3. Three copolymers were synthesized using a nonreactive copolyol dimethicone (Silsoft® 475) in Example 3; SM 9 macromer in Example 1, and no silicone additive in Example 2 to observe whether incorporation of the copolyol dimethicone macromers of the invention into a copolymer backbone has any effect on the copolymer properties. The viscosity of each polymer is measured in mucilages. 1 and 2 percent solids content neutralized with AMP-95 at pH 7. In addition, Tg, transparency and turbidity (NTU) values are measured for each polymer. Results are reported in Table 3A. The viscosity efficiency of the polymer of Example 1 is maintained using 10% by weight of the dimethicone copolyol macromer of the invention. In contrast, ο μΐ of Example 3, which is prepared according to the teachings of US Patent 6,403,074 B1 containing 10% by weight of a non-functionalized copolyol dimethicone has a lower viscosity in both 1 and 2 mucilages. Percent. Non-functionalized copolyol dimethicone (Silsoft 475) could act as a chain transfer agent in Example 3a and cause the viscosity deficiency of the resulting associative polymer.

Examples of 4 to 6 Emulsion polymers are prepared as in Examples VI to VIII using the monomers and macromers shown in Table 4.

The comonomers of Examples 4 and 5 are copolymerized in the presence of olefinically unsaturated copolyol dimethicone macromers of the invention, while the comonomers of comparative Example 6 are polymerized in the presence of a nonreactive (i.e., saturated copolyol dimethicone carboxylate). Polymers are compared for relative viscosity performance. hydrophobic onomer semihydrophobic monomer The gel properties of each polymer are measured [with] mucilages with 1 and 2 percent solids neutralized with AMP-95 at pH 7. When unsaturated functional copolyol dimethicone macromers (SM 9 and SM 7) are copolymerized on the associative polymer backbone, said polymers overcome the typical phenomenon of viscosity depression presented by associative polymers containing saturated copolyol dimethicone (SM 6) as shown in Table 4A below. The glaze transition temperature and mucilage transparency values were maintained.

Examples of 7 to 10 Emulsion polymers are prepared as in Examples VI to VIII using the monomers and macromers shown in Table 5.

In these examples the loading effect of cyclic anhydride with respect to dimethicone copoliol on the synthesis of dimethicone copoliol macromer on the gel properties of the final copolymer product is determined and reported in Table 5A.

The gel properties of each polymer are measured in 1 and 2 percent solid content mucilages neutralized with AMP-95 at pH 7. From the data in Table 5A, polymers polymerized from synthesized anhydride loading macromers to dimethicone charges Copoliol of 0.25 to 0.75 equivalents (based on the OH index of dimethicone copoliol) gives optimal gel properties.

Examples 11 and 12 Emulsion polymers are prepared as in Examples VI to VIII using the monomers and macromers shown in Table 6.

Two copolymers were polymerized using the monomers and macromers shown in Table 6. The reactive copolyol dimethicone macromers of Examples SM 5 and SM 7 are synthesized of dimethicone copolyols with different molecular weights (MW = 2,500 and 19,000, respectively). Synthesized copolymers of low and high molecular weight dimethicone copoliol macromers give good sensory and gel properties. Associative monomer Semi-hydrophobic monomer The gel properties of each polymer are measured in mucilages with 1 and 2 percent solids neutralized with AMP-95 at pH 7. The data are presented in Table 6A.

Examples of 13 to 20 Emulsion polymers are prepared as in Examples VI to VIII using the monomers and macromers shown in Table 7.

Several non-associative copolymers are synthesized using dimethylone copolyol macromers containing pendant terminal polyether groups which are fully terminated with an unsaturated carboxylate group (R = R '= cyclic anhydride radical in Formula Illa; z = y in Formula Via) or partially functionalized with an unsaturated carboxylate group (one of R or R 1 = hydrogen in Formula IIIa; z <y in Formula Via). The viscosity of each polymer is measured in mucilages with 1 and 2.5 percent solids neutralized with AMP-95 at pH 7.

In addition, the Tg, transparency, and turbidity (NTU) values for each polymer are measured. Results are reported in Table 7A.

Examples of 21 to 54 Emulsion polymers are prepared as in Examples VI to VIII using the monomers and macromers shown in Table 8. The viscosity of each polymer is measured in mucilages with solids contents of 2, 3, and 5 percent. neutralized with AMP-95 at pH 7.

Additionally, Tg, transparency and turbidity (NTU) values are measured for each polymer. Results are reported in Table 8A.

Examples of 55 to 59 Acid-swellable cationic associative emulsion polymers are polymerized from the monomers and macromers shown in Table 9 according to the following procedure.

A monomer emulsion is prepared by adding (with mixing) the monomers in Table 9 in a reactor containing about 340 parts by weight of water, about 5.5 parts by weight of Emulsogen® EPN 407 nonionic surfactant and about of 0.3 part by weight of anionic sodium lauryl sulfate surfactant (30%). The resulting mixture is stirred (about 400 rpm) at a temperature in the range of about 20 to about 25 ° C under a nitrogen atmosphere until an emulsion is obtained. A solution of about 0.12 parts by weight of Bruggolite® FF6 (reducing agent) in about 5.0 parts by weight of water is then added to the stirred mixed monomer emulsion to initiate the polymerization reaction. A solution of about 0.16 parts by weight of sodium persulfate (oxidizing agent) in about 5.0 parts by weight of water is then added to the stirred mixed monomer emulsion to initiate the polymerization reaction. The temperature of the reaction mixture is maintained at a temperature in the range of about 60 to about 70 ° C for about 2.5 hours after addition of the initiator. Additional amounts of initiator are added at about 0.5 hours and about 1.5 hours after the reaction starts (about 0.08 parts by weight of sodium persulfate in about 3.0 parts by weight of water). for each additional amount of initiator added). The resulting polymer emulsion is cooled to a temperature in the range of about 44 to about 46 ° C over a period of about 45 minutes and thereafter an oxidizing solution is added to the reaction mixture in two portions. at one hour intervals. Each oxidizing solution (redox) contains about 0.15 part by weight t-butyl hydroperoxide (70%), about 0.015 part by weight sodium lauryl sulfate (30%) and about 0.15 part by weight Bruggolite® FF6 of reducing agent in about nine parts by weight of water. Polymer emulsions are cooled to room temperature and discharged from the reactor. Associative onomer The viscosity and transparency properties of each of the polymers are measured in mucilages with 2 percent solids content neutralized to pH 4 with a 50 percent glycolic acid solution. Results are reported in Table 9A.

Example 60 Several hair-fixing gel compositions are formulated using the dimethicone copolyol-containing polymers, carbomer rheology modifiers, and other components identified in Table 10.

The gel compositions are formulated as follows: The rheology modifier is dispersed in water and mixed giving a uniform dispersion. The rheology modifier dispersion is partially neutralized with AMP-95 at pH 6. The copolyol dimethicone polymer emulsions (5 wt% as supplied, or 1.5 wt% polymeric solids) synthesized according to the given examples. in Table 10A, are slowly added to the dispersion with intimate mixing and neutralized to a final pH of 7. A preservative is then added to the neutralized composition. Transparency and viscosity values are measured for each gel sample. Results are reported in the table below.

Example 61 A hair fixative composition is formulated from the polymer of Example 24 (2.0 wt% polymer solids) using the ingredients and procedure set forth in Example 60, except that no rheology modifiers are present. For comparison purposes, a commercially obtainable fixing polymer, Luviskol K90 polymer, is similarly formulated (2.0% by weight polymeric solids) except that no neutralization has been performed.

The ability of fixative formulations to fix a hair model under conditions of extreme humidity is evaluated. Hair models are prepared and evaluated according to the dummy head hair model selection test described above. Two mannequin heads, one implanted with Asian hair and the other implanted with Caucasian hair, are used in the test. The hair bundles used to model the tips and curls on the Asian-dummy head have lengths of approximately 2.5 inches (6.35 cm) and 4 inches (10.16 cm), respectively. The hair bundles used to model the tips and curls on the Caucasian-haired mannequin head have lengths of approximately 4 inches (10.16 cm) and 5 inches (12.7 cm), respectively. The hair bundles used to model the tips and curls found on the Asian dummy head are treated with 0.8 g / bundle of the experimental and commercial fixer, and the hair bundles used to model the tips and curls that fit found on the dummy head with caucasian hair are treated with 0.5 g / beam of experimental and commercial fixative. Asian hair is naturally coarser and denser per unit area of the dummy's scalp.

Consequently, more fixative is used to maintain the initial modeling.

After drying, the shaped portions of both mannequin heads are rigid and firm to the touch (Figures 1 and 1a). Both heads of dummies are placed in a humidity chamber (35 ° C to 95% relative humidity) for a period of 3 hours. At one hour intervals, each dummy head is removed from the humidity chamber and each side is assessed for retention of the modeling fixation and photographed (Figures 1/1 A through 4 / 4A). From the photographs shown in Figures 2 and 2A, it is evident that the commercial fixative composition begins to fail after the first hour of exposure to high humidity conditions because the curls on both Caucasian and Asian-haired mannequins unroll, and the tips on the Asian hair dummy begin to collapse.

As illustrated in Figures 3, 3A, 4 and 4A, curl and tip retention is maintained after 2 and 3 hour exposure to high humidity conditions in the case of Asian hair and curl retention is demonstrated in the hair. case of Caucasian hair, for the polymer of the invention. For the same exposure ranges, the commercial fixative polymer composition shows no curl retention, although the tips are beginning to sag.

After exposure for 3 hours in the humidity chamber, modeling using the polymer of the invention is more rigid, harder and tougher than in the case of commercial polymer. It is observed that the modeling presents good radiance and soft feel to the touch.

Example 62 The polymers obtained in Examples 4, 21, 23, 25, 30, 35, and 47 are formulated into fixative compositions according to the procedure of Example 60 except that different amounts of gel are indicated in Table 11.

For comparison purposes, a commercially obtainable fixing polymer, Luviskol® K90 PVP, is similarly formulated at pH 7.

After formulation, repetitions of the fixative compositions for curl retention under high humidity conditions are evaluated via the HHCR test described above. Results are shown below in Table 11. 1 Average 5 repeats 2Average 9 repeats 3Formulated with 0.3 wt% Carbopol® Ultrez rheology modifier 21 Example 63 A fixative gel is prepared from the polymer of Example 35 (3 % by weight of polymeric solids) according to the procedure outlined in Example 60. Carbopol® Ultrez 21 is used as a rheology modifier. For comparison purposes, a commercially obtainable fixative polymer, Luviset® Clear transparent fixative polymer (3 wt% polymer solids), is similarly formulated at pH 7. The experimental gel is prepared, tested and evaluated according to the protocol. from HHSR above. The results are illustrated below in Table 12. The reported stiffness retention values (% SR) represent an average of 5 repetitions for the experimental fixative polymer and also for the comparative PVP fixative polymer. Formulated with 0.3 wt% Carbopol® Ultrez rheology modifier 21 Example 64 A fixative gel is prepared from the polymer of Example 35 (2 wt% polymer solids) according to the procedure outlined in Example 60. Carbopol® Ultrez 21 polymer is used as a rheology modifier. For comparison purposes a commercially obtainable fixing polymer, Luviset® Clear transparent fixing polymer (2 wt% polymer solids) and Luviskol® K90 PVP (2 wt% polymer solids) are similarly formulated at pH 7. Experimental gel is prepared, tested and evaluated according to the HHSCR protocol above. Results are shown below in Table 13. Reported spiral curl retention values (% SCR) represent an average of 5 repetitions for the experimental fixative polymer and also for the PVP fixative polymer. comparative. ‘Formulated with 0.3% by weight of Carbopol rheology modifier” Ultrez 21.

Example 65 Hair gel formulations containing the polymers of the invention are formulated as shown in Example 60 except that the amount of fixative polymer used comprises from 1 to 5% by weight (polymeric solids) as shown in Table 14 and no modifier was used. of rheology. Commercially obtainable polymers are also formulated known for hard fixative properties. Treated Asian-like hair samples (0.8 g of fixative composition / sample) are also prepared and evaluated for mechanical stiffness after exposure to 50% and 90% relative humidity conditions as described above in the method of mechanical stiffness test. Five replicates of each test sample are prepared and tested. The average peak force for the 5 replicates is calculated and recorded.

The data in Table 14 demonstrate that the fixative polymer embodiments of the invention exhibit mechanical stiffness values ranging from 3 to 11.4 Newtons at 50% relative humidity (slightly soft fixation to super hard fixture modeling performances). Commercial fastener polymers (eg, Luviskol® and Luviset® Clear fasteners) have mechanical stiffness values of 6.5 to 7.8 Newtons, equivalent to hard and super hard fixture modeling ratings, but higher concentrations (e.g. 5 wt%) of polymer solids as required to obtain these values. At lower concentrations of polymer solids (eg, 2% by weight) these commercial polymers exhibit reduced peak strength values compared to the present polymers.

Example 66 Hair gel formulations containing the polymers of the invention are formulated as shown in Example 60 with the amount of fixative polymer (wt% polymer solids) shown in Table 15. Commercially obtainable polymers are also formulated known for the fixative properties of hard fixation. Both the experimental fixative polymer and the commercially obtainable fixative polymer are formulated with 0.3 wt% (based on the total weight of the formulation components) Carbopol® Ultrez 21 rheology modifier. In addition, comparative tests are also performed using trademark hair care products. Treated Asian-type hair samples (0.8 g of fixative composition / sample) are prepared and evaluated for mechanical stiffness after exposure to 50% and 90% relative humidity conditions as described above in the stiffness test method. mechanical. Five replicates of each test sample are prepared and tested. The average peak force for the 5 replicates is calculated and recorded for each as shown in the Table below.

Mechanical stiffness values obtained for polymers of the invention (tested at 2 wt% polymeric solids with 0.3 wt% Carbopol® Ultrez 21 rheology modifier, weights based on total composition weight) comprise from 5.8 to 7.7 Newtons (mean peak flexion force). Experimental polymers exhibit hard clamping modeling performances with super hard clamping at 50% relative humidity.

Mechanical stiffness values obtained for inventive polymers (tested at 2 wt% polymer solids with 0.3 wt% Carbopol® Ultrez 21 rheology modifier, weights based on total composition weight) comprise from 5.4 to 6 .5 Newtons (mean peak bending force) providing longer lasting modeling performance with hard clamping Very hard clamping at 90% relative humidity with excellent moisture resistance. The rheology modifier improves the mechanical stiffness of all fixing polymers as illustrated when comparing the stiffness data in Table 14 (in the rheology modifier) with the stiffness data in Table 15 (with rheology modifier).

Commercial fixative polymers provide mechanical stiffness at 50% relative humidity in the range 3.2 to 6.7 Newtons (medium peak force), indicating hard-to-fast fixation modeling. However, mechanical stiffness values fall dramatically (except Fixate® PLUS, Fixate® G 100 polymers from Noveon and Acudyne ™ SCP from Rohm and Haas) at 90% relative humidity, indicating poor moisture resistance properties.

Commercially obtainable finished modeling gel products from Procter & Gamble, LOreal, and Unilever also feature mechanical hardness to hard-to-fasten hardness ratings (except LOreal's Studio line fusion gel), but these commercial products are optimized and contain very high levels of polymer solids including fixing polymers and other fixing ingredients with more than 2.3% by weight of polymer solids.

The following examples illustrate the use of the present polymers to formulate various hair care embodiments of the invention.

Example 67 This example illustrates the use of the polymer synthesized in Examples 4, 10, 20, 28, 35, and 45 in a curl-enhancing cream hair gel formulation shown in Table 16. The rheology modifier is homogeneously dispersed in water. DI and pre-neutralized with AMP-95. The polymer of Examples 4, 10, 20, 28, 35, and 45 is slowly added to the pre-neutralized dispersion, carefully mixed and neutralized with more AMP-95. The ingredients in Parts B, C, D and E are formulated separately and then added in alphabetical order to the Part A dispersion and mixed. The resulting gel formulation has an opaque gold appearance, a pH above 6.3 and a viscosity greater than 15,000 mPa s.

Example 68 This example illustrates the formulation of a high solids salon styling gel using the polymer of Examples 4, 10, 20, 28, 35, and 45. The following ingredients are used to formulate the modeling gel . Deionized water is weighed into a vessel and the experimental polymer is slowly added with mixing until a homogeneous dispersion is formed. Ingredients 3 to 8 are slowly added with mixing in the numerical order indicated in the Table. When a homogeneous dispersion is obtained, the formulation is neutralized with ingredient 9 at a pH value of about 6.5. The resulting silica gel formulation has a transparent appearance (transparency value (% T) greater than 90%), and a viscosity greater than 10,000 mPa s. The gel has excellent flow characteristics with a smooth, silky feel.

Example 69 This example illustrates the formulation of a low solids, low viscosity transparent salon modeling gel using the polymers of Examples 4, 10, 20, 28, 35, and 45. The following ingredients are used for formulate the modeling gel.

Deionized water is weighed into a vessel and the rheology modifier is sprayed into the vessel and allowed to hydrate and then mixed to form a uniform dispersion. The inventive polymer is slowly added with mixing until a homogeneous dispersion forms.

Ingredients 3 to 9 are slowly added with mixing in the numerical order indicated in the Table. When a homogeneous dispersion is achieved, the formulation is neutralized with ingredient 10 to a pH value of about 6.5. The gel formulation obtained is subjectively compared to the high solids gel of Example 68 and was found to be equally transparent but less viscous.

Example 70 A funky (pigmentable, easy-to-sculpt) hair gel is formulated with the polymer of Examples 4, 10, 20, 28, 35, and 45. This composition demonstrates the ability of the present polymers to be formulated with ethanol, emollients and a texture modifier. The following ingredients are used to formulate the gel. Deionized water is weighed into an appropriate vessel, and the rheology modifier is homogeneously dispersed in D.I. and then the polymer of Examples 4, 10, 20, 28, 35, and 45 is dispersed in the dispersion. The Part B ingredients are added to the Part A dispersion in the order indicated in the Table concluding with the addition of ingredient 8. The Part C ingredients are formulated separately and then added to the Part A dispersion with incremental mixing. Additional AMP-95 (if necessary) is added to bring the pH value to about 6.5. The resulting gel formulation has a blue appearance, a viscosity value of about 28,000 mPa s and an elastic, sticky consistency.

Example 71 The following high transparency hair gels demonstrate the ability to use the present rheology modifier polymers to prepare soft, low viscosity gels. The polymers of Examples 20, 35, and 45 are each formulated according to formulations A, B, and C shown in the table below (9 formulations in all).

Each formulation is prepared as follows. The rheology modifier is dispersed in water D.I. and mixed until uniform dispersion is obtained. Then the aqueous dispersion is partially neutralized with triethanolamine. Then the ingredients of numbers 4 to 8 are then slowly added in numerical order with stirring until a homogeneous dispersion is formed. The pH of the dispersion is adjusted to about 6.5 with more triethanolamine to give low viscosity soft gels. All formulations are transparent (> 90% T) with a viscosity of <20,000 mPa s.

Example 72 Hair gels are formulated from the polymers of Examples 20, 35, and 45. Each polymer is formulated according to formulations A, B, and C as shown in the table below (9 formulations in all) demonstrating that it is possible. obtain transparent gels with medium viscosity. The formulation procedure of Example 71 is repeated for medium viscosity gels.

All formulations are transparent (> 90% T) with a viscosity of <45,000 mPa s. Example 73 Hair gels are formulated from the polymers of Examples 20, 35, and 45. Each polymer is formulated according to formulations A, B, and C presented in the table below (9 formulations in all) demonstrating that it is possible to prepare high viscosity transparent gels by increasing the weight% of polymeric solids. The formulation procedure of Example 71 is repeated for the high viscosity gel compositions.

All formulations are transparent (> 90% T) with a viscosity> 45,000 mPa s.

Example 74 Hair gels are formulated from the polymers of Examples 20, 35, and 45. Each polymer is formulated according to formulations A, B, and C shown in the table below (9 formulations in all).

Each formulation is prepared as follows. The rheology modifier is dispersed in water and mixed until a uniform dispersion is obtained. Then the aqueous dispersion is partially neutralized with AMP-95. Then ingredients numbered 4 to 10 are slowly added in numerical order with stirring until a homogeneous dispersion is formed. The pH of the dispersion is adjusted to about 6.5 with more AMP-95 giving soft, low viscosity gels.

Example 75 This formulation demonstrates the ability to create a wax formulation using the polymer of Examples 4, 10, 20, 28, 35, and 45 with oil and a mixture of surfactants and emulsifiers. Each polymer is formulated with the ingredients shown in the table below.

The ingredients of Part A are combined with mixing and heated to 70 ° C. In a separate vessel, the ingredients of Part B are combined with mixing and also heated to 70 ° C. Part B is combined with Part A, mixed and heated at 70 ° C for 5 minutes. The pH of each formulation is adjusted to approximately 6.5 and a semi-solid waxy gel is obtained.

Example 76 This example demonstrates the formulation of a cluster enhancing cream gel using the polymer of Examples 4, 10, 20, 28, 35, and 45 and a guerbet ester as a radiance / gloss enhancer.

Each polymer is formulated with the ingredients shown in the table below. The rheology modifier is uniformly dispersed in D.I. water. Ingredients 3 to 6 are added in numerical order and mixed until a uniform dispersion is obtained. The dispersion is neutralized at a pH of approximately 6.3 when a creamy white gel is obtained. The gels have a viscosity of about 33,000 mPa s and are shiny in appearance.

Example 77 Hair spray compositions using the polymer of Example IV are prepared in aqueous and hydroalcoholic formulations (propellant compatible) using the ingredients set forth in the table below.

Hair spray compositions are prepared as follows using conventional mixing techniques.

Formulation A: A batch of 400 g of 5% aqueous active polymer solution is dispersed in D.I. with 0.2% preservative and measured for transparency and turbidity properties.

Formulation B: A 200 g sample of 5% active polymer is dispersed in ethanol and measured for viscosity, transparency and turbidity properties.

Both aqueous and solvent-based hair spray formulations have viscosity values sufficiently low to be sprayable. Each of the formulations provides good modeling properties with excellent fixation.

Example 78 This example exemplifies the use of the present polymers to formulate a hair styling mousse. Each of the polymers of Examples VI, 35, and 45 is formulated with the ingredients set forth in the table below to formulate hair styling mousse compositions.

The polymers are formulated as follows. Mix Part A with agitation and combine with the components of Part B in the order listed before neutralizing to pH 6. Composition AB is loaded into an appropriate pressurizable container (polymer coated aluminum can) that is hermetically sealed with a valve. of mousse positioned on top of can. Vacuum is applied to the can to evacuate the top space. Then the valve is fixed in place and the can is loaded with the propellant mixture (ingredient No. 10) through the valve stem.

In another embodiment of the invention, polymers containing polymerized repetitive units of the copoliol dimethicone macromers may be used in rinse-type hair shampoo, shampoo conditioner, 2-in-1 shampoo, color maintenance color, shampoo after coloring, analogs). These shampoos confer hair styling and "body" benefits without compromising shampoo's cleansing and / or conditioning attributes. "Body" benefits include root lift, increased capillary volume, elasticity, control (i.e. ease of shaping) and combability, i.e. maintenance of shaping without negative sensory sensation. Said body attributes are particularly attractive to people with thin or long, heavy hair.

Formulations for surfactant cleaning applications, such as shampoos (e.g., 2-in-1 shampoos, dandruff shampoos), shower gels, body wash, and the like) incorporating the polymers of the present invention. they may comprise an anionic surfactant, nonionic and zwitterionic surfactant, an amphoteric surfactant or mixtures of mono and polymeric quats for conditioning; silicones for conditioning; rheology modifiers; thickeners; suspending agents; preservatives; fragrance / effluent solubilizer; dyes; pigments, neutralizers or pH adjusters; botanists; vitamins; chelating agents; foam enhancers; pearls; air bubbles; mica; organic and inorganic pearling agents; Water; viscosity reducers; hydrotropic; alcohols; anti-dandruff actives; salt and combinations thereof.

Example 79 Separate transparent shower gel compositions with suspended beads are formulated with the polymers of Examples 13, 20a, 20b, and 20c. The ingredients and quantities are presented in the table below.

Each shower gel composition is formulated by dispersing the respective experimental polymer in water D.I. Sodium lauret sulfate surfactant with gentle mixing is added to the dispersed polymer. The Part A component is neutralized with NaOH at pH 6.5. The ingredients of Part B are added to the Part A mixture in numerical order with mixing. The pH of the final composition is adjusted to 6.5 if necessary. Each of the shower gel compositions is evaluated for viscosity, yield and turbidity properties, as well as for suspension stability. Among the properties presented in the table below, gels have good properties of transparency, rheology and suspension stability (i.e., the ability to suspend solid particles over long periods of time).

Example 80 The following formulation is an example of a temporary colorant shampoo or color maintenance shampoo using the polymers of Examples 13, 20a, 20b, and 20c. Shampoo demonstrates a temporary viscous stable composition of hair dyes using cationic dyes; excellent suspension and stabilization of a pearlescent material with a pronounced pearly aspect; improved rheological and sensory properties.

The ingredients of Part A are combined and carefully mixed. In a separate vessel, the ingredients of Part B are formulated by dissolving disodium EDTA in D.I. hot (approximately 50 ° C). The remaining Part B ingredients (from 5 to 9) are added in numerical order with gentle mixing. Part B is slowly added to Part A with moderate agitation. The pH of the combined composition is adjusted to 7.0. The ingredients of Part C are combined in a separate vessel by first dissolving the dyes (ingredients 11 through 13) in D.I. hot (approximately 50 ° C). Then dimethicone copolyol is added to the dye solution. Part C is combined with Part AB with careful agitation. Ingredient Part D # 17 is pre-dispersed in water D.I. and is combined together with ingredient No. 15 in the composition of Part ABC and mixed.

Example 81 This example illustrates the formulation of a conditioner anti-dandruff shampoo using a polymer embodiment of the invention. The composition is formulated by the back-acid technique described herein.

The ingredients of Part A are combined by dispersing the polymer of Examples 13, 20a, 20b, and 20c in water D.I. The surfactants, ingredients with num. 3 and 4 are added to the dispersion with careful stirring to minimize entrapment of air bubbles. Part A is then neutralized with ingredient No. 5 at a pH of 6.5. The ingredients from Part B are combined in a separate vessel and heated to 45 ° C to aid dissolution of the conditioner, ingredient No. 7, Part B is added to Part A and mixed. The Part C surfactant, ingredient # 9, is added to Part AB and ingredient # 10 is used for back-acid adjustment to pH 5.5.

The remaining Part C ingredients, num. from 11 to 14, are added in numerical order to the thickened Part ABC composition.

Sodium chloride, ingredient # 15, is added to adjust the viscosity of the formulation. The obtained anti-dandruff shampoo is stable and is capable of suspending the insoluble anti-dandruff agent, zinc pyrithione, without any sedimentation.

Example 82 The polymers of the present invention containing surfactant silicone moieties may be used in a variety of leave-on and rinse-off cosmetic formulations as hair treatments, hair lotions, hair tonics, hair rinses, hair emulsions, damaged tip treatment fluids, permanent wave equalizers, hot oil treatment preparations, conditioners, and the like. The following example illustrates the use of the polymer embodiments of the invention in the formulation of a creamy conditioner compatible with monomeric quaternary compounds, emulsifiers and fatty alcohol emollients. The ingredients of the composition are presented in the table below.

Deionized water (ingredient # 1) is heated to 65 to 67 ° C.

The remaining Part A ingredients (numbers 2 to 4) are added to the hot water and mixed thoroughly. In a separate vessel, the ingredients of Part B are combined under mixing and heated to 65 to 67 ° C. Part B

It is combined with Part A and mixed until a uniform dispersion is obtained. The dispersion of Part AB is cooled to 40 ° C. Add ingredient No. 9 and continue mixing. The pH is adjusted with ingredient No. 10 to 4.0. The viscosity and appearance properties of the compositions are given in the table below.

Example 83 This example illustrates the formulation of a conditioner anti-dandruff shampoo using the cationic polymer embodiments and ingredients set forth in the table below. Each polymer is formulated separately.

Parts A and B are formulated in separate vessels with agitation to give uniform mixtures. Part A is slowly combined with Part B with mixing. The ingredients of Part C (5 through 14) are mixed in the composition of Part AB in numerical order and mixed until a uniform mixture is obtained. The pH of the ABC composition is adjusted with ingredient 15 to a pH value between 4.9 and 5.3 inclusive. Stable shampoo compositions are obtained.

Example 84 The following formulation is an example of a facial wash conditioner. It demonstrates a formulation with stable aqueous surfactant composition at low pH using salicylic acid. Each polymer is formulated with the ingredients listed in the table below.

In a mixing vessel the ingredients of Part A (1-3) are combined in the order listed in the table and mixed evenly. The mixture is pre-neutralized with citric acid. The ingredients from Part B are mixed in a separate vessel and combined with Part A. The ingredients from Part C (8 to 15) are added to the Part AB mixture in the order listed and mixed until a uniform composition is obtained. The pH of the Part ABC formulation is adjusted with the ingredient of 15 to pH 4.0. A stable facial wash product is obtained.

Example 85 This example demonstrates the preparation of a clear conditioning shampoo containing a mixture of silicones, cationic and botanical materials in a low pH formulation. The ingredients and formulation procedure are presented below.

Part A is formulated by adding ingredient No. 2 in water D.I. and mixed until uniform dispersion is obtained. Ingredients num. 3 to 5 are added to the dispersion and this is mixed. Part A is slowly combined with Part B and mixed. Ingredients from Part C, nums. from 7 to 18 are added in the order listed and mixed until a uniform mixture is obtained. The pH is adjusted with ingredient No. 19 to 5.0. A stable and homogeneous shampoo is obtained.

Example 86 This example illustrates the formulation of a body lotion composition using the polymer of Examples 13, 20a, 20b, 20c, and 20d. The components of the composition are presented in the table below.

The ingredients of Part A are placed in a vessel in the indicated numerical order and heated to 65 to 70 ° C under vacuum stirring for 20 minutes. The mixture is cooled to 60 ° C and the polymer of Examples 13, 20a, 20b, 20c, and 20d is added to the formulation. The pH is adjusted to about 6.8 with ingredient No. 9 and the formulation is cooled to 50 ° C. Ingredient No. 10 is then added with mixing and the formulation is cooled to 40 ° C. Ingredient No. 11 is added and mixed until a homogeneous composition is obtained.

Example 87 This example illustrates the use of the cationic polymer of Examples 56 to 59 in the formulation of a hair conditioner gel.

The ingredients and method of preparation are presented below.

Ingredient No. 1 is dispersed with mixing in water D.I. until a uniform mixture is formed. Ingredients num. from 2 to 6 are added in numerical order and mixed. The pH of the mixture is adjusted to about 4.0 and the formulation is mixed until a homogeneous gel forms. The properties of the gel are presented in the table below.

Fixative compositions are evaluated for curl retention under high humidity conditions in hair bundles (9 repetitions / composition) via the test (HHCR) described above. The results are illustrated in the table below.

Example 88 A clear shower gel with the ingredients shown in the table below and using the back-alkaline formulation procedure.

Each of the polymers of Examples 56 to 59 is dispersed in deionized water (ingredient # 1) and mixed until a homogeneous dispersion is obtained. Ingredients num. 2 and 3 are then added with mixing.

Ingredient No. 6 is added to the dispersion and this is mixed. The pH of each formulation is adjusted to pH 6.0 with citric acid (ingredient # 7) to increase the viscosity of the composition. One sample of each composition is tested for viscosity properties. The pH of each composition is adjusted via back alkaline with sodium hydroxide (ingredient # 8) and the viscosity properties are again recorded as shown in the table below.

An exemplary embodiment of the invention relates to a composition comprising: (I) a polymer formed from polymerization of a monomer mixture comprising: a) at least one silicone-containing macromer selected from Formula III, Illa, IV, and Via above in optimal combination with a monomer selected from: (b) at least one nonionic monomer; c) at least one acid vinyl monomer; d) at least one cationic vinyl monomer; e) at least one associative vinyl monomer; f) at least one semihydrophilic vinyl monomer; g) a cross-linking monomer; and mixtures thereof; and mixtures thereof; (II) an ingredient selected from water, a surfactant, a rheology modifier, and mixtures thereof; optimally combined with (III) one or more components selected from chelators, conditioners, diluents, fragrances, pigments, dyes, antioxidants, skin and hair moisturizing conditioners, lubricants, moisture barriers and emollients, neutralizers, opacifiers, pharmaceutical actives, preservatives, solvents, spreading aids, sunscreens, surfactants, conditioning polymers, vitamins, viscosity adjusters, viscosity modifiers, neutralizing agents, pH adjusting agents, and emulsifiers.

In another exemplary embodiment of the invention the silicone-containing macromer is represented by the formulas: and isomers thereof, wherein R ', R1, R2, R3, R4, R5, R6, EO (OE), ΡΟ (ΟΡ), a, b, c, η, χ, y and ζ are as previously defined.

Example 89 A washable hair styling wax is formulated with the ingredients shown in Table 43.

The ingredients of Part A are mixed and heated to 75 ° C.

The ingredients of Part B are mixed and heated to a temperature of 70 to 80 ° C for a period of time until the ingredients have completely melted and a homogeneous mixture is obtained. Part A is slowly added to Part B with continuous mixing at 300 to 500 rpm while maintaining the temperature between 70 ° and 80 ° C. The components of Part A and Part B are mixed until a uniform mixture is formed. The mixture of Part AB is allowed to cool to a temperature between 60 ° and 70 ° C. The ingredients of Part C are combined and are added to the Part AB mixture while maintaining the temperature of the mixture between 60 ° and 70 ° C. The ingredients of Part D are combined and added to the Part ABC mixture with mixing until a uniform mixture is formed. The Part ABCD mixture is allowed to cool to 50 ° C after which the Part E ingredients are sequentially mixed into the mixture. The pH value of the composition is determined to be pH 7.4. The mixture is allowed to cool to 40 to 45 ° C, poured into a container and allowed to solidify to give the hair wax product. The product looks shiny to dirty white. The product is allowed to stand for a period of 24 hours at which point Brookfield viscosity of the product at 40 ° C at 20 rpm is measured using a # 7 spindle determined to be 150,000 mPa s. .

Example 90 A transparent-looking hair wax is formulated with the ingredients set forth in Table 44. The formulation provides a defined but malleable hair styling and provides a non-greasy look and feel as well as a transparent look when applied to the hair. Disodium EDTA is dissolved in glycerine and the remaining Part A ingredients are added to the solution. The mixture of Part A The mixture is heated to 80 ° C with slow stirring mixing until a uniform mixture is formed. The Part A mixture is cooled while stirring at 60 ° C. Part B is added to Part A and mixed until smooth. The Part AB mixture is neutralized with Part C. Under moderate agitation, the ingredients of Part D are added and mixed until uniform. The ABCD composition is stirred slowly and allowed to cool. When the batch cools to a temperature of 40 ° to 45 ° C it is poured into a wide mouth container and allowed to cool. The clear-looking hair wax product is allowed to stand for a period of 24 hours, at which point Brookfield viscosity is measured at 25 ° C at 20 rpm using a # 7 spindle and determined to be 150,000 mPa. s.

Example 91 Hair styling balms incorporating color, mica and / or glitter are formulated from the ingredients shown in Table 45. The formulation promotes better washability, less residue buildup, longer lasting fixation, and a non-greasy feel to the hair.

Additionally, when the formulation is applied to the hair, it exhibits excellent stiffness properties without the concomitant noise and excessive waxy residues intrinsic to commercially obtainable waxy hair products present.

The ingredients of Part A are mixed and heated to about 75 ° C. The ingredients of Part B are mixed and heated to a temperature of 70 to 80 ° C for a period of time until the ingredients completely melt, and a homogeneous mixture is obtained. Part B is slowly added to Part A with continuous mixing at 300 to 500 rpm while maintaining the temperature between 70 ° and 80 ° C. The components of Part A and B are mixed until a uniform mixture is formed. The mixture of Part AB is allowed to cool to a temperature between 60 ° and 70 ° C. The Part C ingredient is added to the Part AB mixture while maintaining the temperature of the mixture between 60 ° and 70 ° C. The Part D ingredient is added to the Part ABC mixture with mixing until a uniform mixture is obtained. The combination of Part ABCD

is maintained at about 60 ° C, after which the ingredients of Part E and Part F are added sequentially with mixing to obtain a homogeneous mixture. The pH value of the composition is determined to be 7.3. The composition is allowed to cool to a temperature between 40 ° and 45 ° C, poured into a container and allowed to solidify giving the hair wax product.

Claims (24)

Composition, characterized in that it comprises: A) a polymerized polymer of a monomer composition comprising at least one copolyol dimethicone macromer selected from formulas III and IV: wherein, in formula III, R and R 'independently represent hydrogen and a cyclic anhydride radical, with the proviso that ReR 'do not both represent hydrogen at the same time, ReR independently represent a radical selected from C1 to C30 alkyl, halo substituted C1 to C20 alkyl, C3 to C8 cycloalkyl, C 6 to C 14 aryl, and C 2 to C 20 alkenyl, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently from 0 to 100; en is from 0 to 200, E taken together with the oxygen atom to which it is attached represents an ethylene oxide radical (EO or OE) and P, taken with the oxygen atom to which it is attached, represents a radical of propylene oxide (PO or OP), where EO and PO radicals may be arranged in a random, non-random, and block order; wherein in the formula IV R and R, E, P, a, b, and c are as defined above, R3 represents a radical selected from C1 to C30 alkyl, halo substituted C1 to C20 alkyl, C3 to C6 cycloalkyl, C6 aryl C14 to C20 to C20 alkenyl, R4 represents a radical selected from C1 to C30 alkyl, C6 to C14 aryl, and C2 to C20 alkenyl, x is 0 to 200, y is 1 to 200, z <y; and wherein said cyclic anhydride radical in formulas III and IV is represented by the formula: wherein R5 and R6 are independently selected from hydrogen and methyl, with the proviso that R5 and R6 both do not represent methyl at the same time; B) at least one solvent or diluent; and optionally C) one or more ingredients selected from surfactant (s), rheology modifier (s), viscosity adjuster (s), emollient (s), humectant (s), lubricant (s), emulsifier (s), conditioner Structurer (s), Fastener (s), Opacifier (s), Spreading aid (s), Antioxidant (s), Sunscreen agent (s), Antiperspirant (s), Pharmaceutical active (s) , vitamin (s), preservative (s), antimicrobial agent (s), antifungal agent (s), botanical extract (s), anti-dandruff agent (s), abrasive (s), chelating agent (s), pH adjusting agent (s), neutralizing agent (s), fragrance (s), pigment (s), coloring agent (s) perloscent (s), propellant (s), oxidizing agent (s), antistatic agent (s), and combinations thereof. Composition according to Claim 1, characterized in that said monomer composition further comprises at least one monomer selected from: a) at least one nonionic vinyl monomer; b) at least one acid vinyl monomer; c) at least one cationic vinyl monomer; d) at least one associative vinyl monomer; e) at least one semihydrophobic vinyl monomer; f) at least one cross-linking monomer; and mixtures thereof. Composition according to Claim 2, characterized in that said nonionic vinyl monomer is selected from at least one monomer represented by the formulas: CH 2 = C (X) Z; CH 2 = CH-0C (O) R 7 wherein X is H or methyl; and Z is -C (O) OR 8, -C (O) NH 2, -C (O) NHR 8, -C (O) N (R 8) 2. -C 6 H 4 R 8, -C 6 H 40 R 8, -C 4 Cl, -C 6 Hn, -C 6 H 7 (R 8) (R 8) (R 8), -CN, -NHC (0) CH 3, -NHC (0) H, N- (2-pyrrolidonyl) , N-caprolactamyl, -C (O) NHC (CH 3) 3, -C (O) NHCH 2 CH 2 -N-ethylenurea, -Si (R 7) 3, -C (O) 0 (CH 2) x Si (R 7) 3, - C (O) NH (CH 2) x Si (R 7) 3, or - (CH 2) x Si (R 7) 3; x is an integer comprising from about 1 to about 6; R independently represents straight and branched C1 to C18 alkyl; R independently represents straight and branched C 1 to C 30 alkyl, hydroxy substituted C 2 to C 30 alkyl, and halogen substituted C 1 to C 30 alkyl. Composition according to Claim 2, characterized in that said acid vinyl monomer contains at least one acid group selected from a carboxylic acid group and salts thereof, a sulfonic acid group and salts thereof, and an acid group. phosphonic acid and salts thereof. Composition according to Claim 4, characterized in that said acid vinyl monomer is selected from acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, alkyl monoesters. C3 to Cis of maleic, fumaric, itaconic or aconitic acid, dicarboxylic acid anhydrides, vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyloxybenzene sulfonic acid, vinyl phosphonic acid, allyl phosphonic acid; 3-acrylamidopropyl phosphonic acid; and salts thereof; and mixtures thereof. Composition according to Claim 1, characterized in that said cationic vinyl monomer is selected from mono- (C1 to C4) alkylamino (C1 to C8) alkyl (meth) acrylate, a di- (C1 to C4) (C1 to C8) alkylamino (meth) acrylate, one (C1 to C4) alkylamino (C1 to 8) alkylamino, one (C1 to C4) alkylamino (C1 to C8) alkylamino acrylamide, a nitrogen containing heterocyclic (meth) acrylamide, a nitrogen containing heterocyclic (meth) acrylate; and salts thereof; and mixtures thereof. Composition according to Claim 6, characterized in that said cationic vinyl monomer is selected from 2- (N, N-dimethylamino) ethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth). ) acrylate, 4- (N, N-dimethylamino) butyl (meth) acrylate, (N, N-dimethylamino) t-butyl (meth) acrylate, 2-t-butylamino) ethyl methacrylate, 2- (N, N- diethylamino) ethyl (meth) acrylate, 3- (N, N-diethylamino) propyl (meth) acrylate, 2-N, N-dimethylamino) neopentyl acrylate, 4-N, N-diethylamino) butyl (meth) acrylate, 2- (N, N-dipropylamino) ethyl (meth) acrylate, 3 -N, N-dipropylamino) propyl (meth) acrylate, 4-N, N-dipropylamino) butyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2- (4-morpholinyl) ethyl methacrylate, 2- (4-morpholinyl) ethyl acrylate, N '- (2-N, N-dimethylamino) ethyl methacrylamide, 2-N, N-dimethylamino) propyl methacrylamide, N'-3 -N, N-dimethylamino) propyl (meth) acrylamide, N- (2-pyridyl) acrylamide, N-2-imidazoyl) (meth) acrylamide, N- (4-morpholinyl) (meth) acrylamide Ν-4-morpholinyl) acrylamide, 2-vinyl pyri dine, 4-vinyl pyridine, N-vinyl-2-methylimidazole, N-vinylimidazole, N-vinyl-4-methylimidazole, and N-vinyloxazolidone; and salts thereof; and mixtures thereof. Composition according to Claim 5, characterized in that said cationic vinyl monomer is selected from 3-trimethylammonium propyl methacrylamide chloride, 3-trimethylammonium propyl acrylamide chloride, de, Ν-dimethylaminoethyl methacrylate with sulfate. C1 to C30 alkyl, Î ±, Î ± -dimethylaminoethyl methacrylate quaternized with methyl chloride, quaternized vinyl imidazole, methacryloyl ethyl betaine, and methacryloyl N-oxide. Composition according to Claim 1, characterized in that said associative vinyl monomer is selected from at least one monomer represented by the formula: wherein each R 9 is independently H, alkyl Q to C 30, -C (0) OH, or -C (O) OR10; R10 is C1 to C30 alkyl; A is -CH 2 C (O) 0-, -C (O) 0-, -O-, -CH 20 -, -NHC (O) NH-, -C (O) NH-, -Ar-CE 2) z-NHC (0) 0-, -Ar- (CE2) Z-NHC (O) NH-, or -CH2CE12NHC (O) -; Ar is a divalent arila; E is H or methyl; z is 0 or 1; k is an integer in the range 0 to about 30, m is 0 or 1, provided that when k is 0, m is 0, and when k is in the range 1 to about 30, m be 1; (Ru-0) n represents a polyoxyalkylene moiety of C 2 to C 4 oxyalkylene units, where R 11 is C 2 H 4, C 3 H 6, C 4 H 8, or a mixture thereof, and n is an integer in the range of about 5 to about 250; Y is -RnO-, -RnNH-, -C (O) -, -C (O) NH-, -RnNHC (O) NH-, or -C (O) NHC (O) -; and R12 is a substituted or unsubstituted alkyl selected from C8 to C40 linear alkyl, C2 to C40 branched alkyl, C8 to C40 carbocyclic alkyl, alkyl substituted C2 to C40 phenyl, a C 2 to C 40 alkyl substituted by aryl, and a C 8 to C 80 complex ester; wherein R11 and R12 optionally includes one or more substituents selected from hydroxyl, alkoxyl, and halogen. Composition according to Claim 9, characterized in that said associative vinyl monomer is selected from polyethoxylated cetyl methacrylate, polyethoxylated cetearyl methacrylate, polyethoxylated (meth) acrylate of arachidyl methacrylate, methacrylate polyethoxylated methyl methacrylate, lauryl polyethoxylated methacrylate, methacrylate lauryl polymethoxylate, methoxy acrylate, polymethoxylated methacrylate (meth) acrylate hydrogenated castor oil polyethoxylate, polyethoxylated canola (meth) acrylate, and polyethoxylated cholesterol methacrylate, the polyethoxylated portion of the monomer containing from about 5 to about 100 repetitive units of ethylene oxide. Composition according to Claim 1, characterized in that said semihydrophobic vinyl monomer is selected from at least one monomer represented by the formula: wherein R 9 is independently H, alkyl Q to C 30, -C (0) OH, or -C (O) OR10; R10 is C1 to C30 alkyl; A is -CH 2 C (O) 0-, -C (O) 0-, -O-, -CH 20 -, -NHC (O) NH-, -C (O) NH-, -Ar-CE 2) z-NHC (0) 0-, -Ar- (CE2) Z-NHC (0) NH-, or -CH2CH2NEIC (0) -; Ar is a divalent arila; E is H or methyl; z is O or 1; k is an integer in the range 0 to about 30, m is 0 or 1, provided that when k is 0, m is 0, and when k is in the range 1 to about 30, m be 1; (Ru-0) n represents a polyoxyalkylene moiety of C 2 to C 4 oxyalkylene units, where R 11 is C 2 H 4, C 3 H 6, C 4 H 8, or a mixture thereof, and n is an integer in the range of about 5 to about 250; Y is -RuO-, -RnNH-, -C (O) -, -C (O) NH-, -RnNHC (O) NH-, or -C (O) NHC (O) -; wherein R11 optionally includes one or more substituents selected from hydroxyl, alkoxyl, and halogen; D is a C 8 to C 30 unsaturated alkyl, or a C 65 to C 30 unsaturated alkyl substituted by carboxy; and R is H or C1 to C4 alkyl. Composition according to Claim 11, characterized in that said semihydrophobic vinyl monomer is represented by at least one monomer of the formulas: CH2 = CH-0 (CH2) a0 (C3H60) b (C2H40) cH CH2 = CH-CH20 (C3H60) d (C2H40) eH where a is an integer of 2, 3, or 4; b is an integer in the range 1 to about 10; c is an integer in the range from about 5 to about 50; d is an integer in the range from 1 to about 10; and e is an integer in the range of about 5 to about 50. Composition according to Claim 1, characterized in that said monomer composition comprises from 0 to 5 weight percent (based on the weight of the total monomers of a cross-linking monomer). Composition according to Claim 1, characterized in that said monomer composition comprises at least 0.01 weight percent based on the total monomer weight of a chain transfer agent. Composition according to Claim 1, characterized in that said composition comprises an ingredient selected from a builder (s), a humectant (s), an emollient (s), a fixative (s), a surfactant (s). ), a rheology modifier (s), a neutralizer (s), a conditioner, and combinations thereof. Composition according to Claim 15, characterized in that said composition further comprises an ingredient selected from an auxiliary solvent, a propellant, and combinations thereof. Composition according to Claim 16, characterized in that said composition is in the form of a cream, ointment, gel, paste, ointment, spray, lotion, squirrel, and mousse. A hair care composition comprising: A) a polymerized polymer of a monomer composition comprising: (i) at least one copolyol dimethicone macromer selected from formulas III and IV: wherein in formula III R and R 'independently represent hydrogen and a cyclic anhydride radical, provided that R and R' both do not represent hydrogen at the same time, R1 and R2 independently represent a radical selected from C1 to C30 alkyl, C1 to C4 alkyl. C20 substituted by halo, C3 to C6 cycloalkyl, C6 to C14 aryl, and C2 to C20 alkenyl, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently from 0 to 100; and n is from 0 to 200, E, taken together with the oxygen atom to which it is attached, represents an ethylene oxide radical (EO or OE) and P, taken with the oxygen atom to which it is attached, represents a propylene oxide radical (PO or OP), where EO and PO radicals may be arranged in a random, non-random, and block order; wherein in the formula IV R and R, E, P, a, b, and c are as defined above, R represents a radical selected from alkyl Q to C30, alkyl from Q to C20 substituted by halo, cycloalkyl C3 to Cg, aryl Ce C14 to C20 to C20 alkenyl, R4 represents a radical selected from C1 to C30 alkyl, C to C14 aryl, and C2 to C20 alkenyl, x is 0 to 200, y is 1 to 200, z <y; and wherein said cyclic anhydride radical in formulas III and IV is represented by the formula: wherein R5 and R6 are independently selected from hydrogen and methyl, with the proviso that R5 and R6 both do not represent methyl at the same time; (ii) at least one acid vinyl monomer; (iii) at least one nonionic vinyl monomer; (iv) at least one associative vinyl monomer; and optionally (v) at least one cross-linking monomer; B) at least one solvent or diluent; C) at least one ingredient selected from the group of a builder, rheology modifier, conditioner, surfactant, emollient, humectant, neutralizer, pH adjusting agent, chelating agent, auxiliary fixative, preservative, a fragrance, a pearlizing agent, and combinations thereof. Hair care composition according to claim 18, characterized in that said structure is selected from at least one wax, at least one fatty alcohol and esters thereof, at least one fatty acid and esters thereof, petrolatum , and combinations thereof. Hair care composition according to claim 18, characterized in that said composition is in the form of a cream, gel, ointment, paste, mousse, spray, or squirt. Hair care composition according to claim 18, characterized in that said acid vinyl monomer is selected from acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid. , C1 to C18 alkyl monoesters of maleic, fumaric, itaconic or aconitic acid, dicarboxylic acid anhydrides, vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyloxybenzene sulfonic acid, vinyl phosphonic acid, allyl phosphonic acid, 3-acrylamidopropyl phosphonic acid; and salts thereof; and mixtures thereof. Hair care composition according to claim 18, characterized in that said nonionic vinyl monomer is selected from C1 to C30 alkyl (meth) acrylates, cyclohexyl (meth) acrylates, 3,3,5 -trimethylcyclohexyl (meth) acrylates, C1 to C30 alkyl (meth) acrylamides, styrene, vinyl toluene butyl styrene, isopropyl styrene, p-chloro styrene, vinyl acetate, vinyl butyrate, vinyl caprolate, vinyl pivalate, neodecanoate vinyl, methacrylonitrile, acrylonitrile, trimethylvinylsilane, dimethylethylvinylsilane, allyl dimethylphenylsilane, allyltrimethylsilane, 3-acrylamidopropyltrimethylsilane, 3-trimethylsilylpropyl methacrylate, 2-hydroxyethyl (HEMA) acrylate, 2-hydroxyethyl (2-hydroxy) -propylate (meth) acrylate; tris (hydroxymethyl) ethane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, N-hydroxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, (meth) acrylamide, t-octyl (meth) acrylamide, N- (2,3-dihydroxypropyl) acrylamide, t-butyl (meth) acrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, methacrylamidoethyl-N-ethylenurea, methoxyethyl (meth) acrylate, 2- (2 -ethoxyethoxy) ethyl (meth) acrylate; and mixtures thereof. Hair care composition according to claim 18, characterized in that said associative vinyl monomer is selected from at least one monomer represented by the formula: wherein each R 9 is independently H, C 1 to C 30 alkyl; C (O) OH, or -C (O) OR 10; R10 is C1 to C30 alkyl; A is -CH 2 C (O) 0-, -C (O) 0-, -O-, -CH 20 -, -NHC (O) NH-, -C (O) NH-, -Ar-CE 2) z-NHC (0) 0-, -Ar- (CE2) Z-NHC (0) NH-, or -CH2CH2NHC (0) -; Ar is a divalent arila; E is H or methyl; z is 0 or 1; k is an integer in the range 0 to about 30, m is 0 or 1, provided that when k is 0, m is 0, and when k is in the range 1 to about 30, m be 1; (Rn-O) n represents a polyoxyalkylene moiety of C 2 to C 4 oxyalkylene units, where R 11 is C 2 H 4, C 3 H 6, C 4 H 8, or a mixture thereof, and n is an integer in the range of about 5 to about 250; Y is -RnO-, -RUNH-, -C (O) -, -C (O) NH-, -RnNHC (O) NH-, or -C (O) NHC (O) -; and R12 is a substituted or unsubstituted alkyl selected from a linear C8 to C40 alkyl, a branched C8 to C40 alkyl, a C8 to C40 carbocyclic alkyl, an alkyl substituted C2 to C40 phenyl, a C 2 to C 40 alkyl substituted by aryl, and a C 8 to C 80 complex ester; wherein R11 and R12 optionally includes one or more substituents selected from hydroxyl, alkoxyl, and halogen. Composition according to Claim 23, characterized in that said associative vinyl monomer is selected from polyethoxylated cetyl methacrylate, polyethoxylated cetearyl methacrylate, polyethoxylated (meth) acrylate, arachidyl polyethoxylated methacrylate, polyethoxylated methacrylate beenila, polyethoxylated lauryl methacrylate, polyethoxylated polyethoxylated (meth) polyethoxylated (meth) polyethoxylated polymethoxylated polymethoxylated methacrylate, methacrylate polyacrylate (meth) polyacetylated acrylate of hydrogenated castor oil, canola polyethoxylated (meth) acrylate, and polyethoxylated cholesterol methacrylate, the polyethoxylated portion of the monomer containing from about 5 to about 100 repetitive units of ethylene oxide.